EP1412578B1 - Dyed and/or printed non-woven fabric - Google Patents

Dyed and/or printed non-woven fabric Download PDF

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Publication number
EP1412578B1
EP1412578B1 EP02747447A EP02747447A EP1412578B1 EP 1412578 B1 EP1412578 B1 EP 1412578B1 EP 02747447 A EP02747447 A EP 02747447A EP 02747447 A EP02747447 A EP 02747447A EP 1412578 B1 EP1412578 B1 EP 1412578B1
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EP
European Patent Office
Prior art keywords
range
nonwoven
process according
component
minutes
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EP02747447A
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German (de)
French (fr)
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EP1412578A1 (en
Inventor
Heike Bartl
Uwe Marg
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Carl Freudenberg KG
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Carl Freudenberg KG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/56—Preparing azo dyes on the material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
    • D06P1/12—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes prepared in situ
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/28—Preparing azo dyes on the material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups

Definitions

  • the present invention relates to a dyed and / or printed nonwoven fabric made of unsplit and / or at least partially split microfibers and / or microfilaments of synthetic polymers containing at least one polyester component and at least one polyamide component and optionally at least one polyurethane component comprising at least one azo dye formed on the nonwoven fabric dyed and / or printed and a method for its coloring and / or printing.
  • Fabric made of plastics textile materials can often be dyed or printed with conventional textile dyeing or textile printing process often in insufficient quality. Difficulties in dyeing or printing arise in particular when the textile material comprises various plastic components, such as polyester and polyamide, since these usually show a very different dyeing behavior, such as BASF "Manual-Dying and Finishing of Polyamide Fibers and their blends with other fibers "B358e / 12.72, page 149.
  • nonwovens which consist of a mixture of microfibers and / or microfilaments, such as polyester / polyamide split fibers, since the split fibers are distributed irregularly in the nonwoven, while in corresponding polyamide / polyester microfiber fabrics, however, usually only a component, generally the weft, consists of polyamide / polyester chippings.
  • the density of the fibers and / or filaments ie the number of fibers and / or filaments per unit area, higher than corresponding fabrics or knitted fabrics, so that for dyeing
  • Such nonwovens require increased amounts of dye.
  • This increased use of dye on the one hand and the uneven distribution of the fibers on the other hand cause that made of several plastic components, dyed or printed nonwoven fabrics of microfibers and / or microfilaments in general have worse color fastness than corresponding fabrics of the same synthetic polymers.
  • DE-OS-25 13 533 describes a process for printing and pad dyeing blended fabric.
  • US Pat. No. 3,081,141 discloses a dyeing process for fabrics and nonwovens, in which first the dye components are applied separately to the substrate to be dyed and subsequently the dye is produced in situ on the substrate.
  • the object of the present invention was therefore to select a suitable class of dyes, which allows the dyeing and / or printing of such nonwoven fabrics of different plastic components with only one class of dyes and thus a dyed and / or printed nonwoven fabric of ungrounded and / or at least partially split microfibers and / or microfilaments of synthetic polymers containing at least one polyester component and at least one polyamide component and optionally at least one polyurethane component to provide, which is characterized by good to very good color fastness, especially washing, welding, water and light and good rub fastness ,
  • This object has been achieved by the provision of a dyed and / or printed nonwoven fabric made of unsplit and / or at least partially split microfibers and / or microfilaments of synthetic polymers containing at least one polyester component and at least one polyamide component and optionally at least one polyurethane component having at least one on the Nonwoven produced azo dye, a so-called development dye, dyed and / or printed.
  • the nonwoven used is a staple fiber nonwoven or a spunbonded nonwoven, preferably a spunbond nonwoven, of un-split and / or at least partially split microfibers and / or microfilaments.
  • the production of corresponding nonwovens can be carried out by customary methods known to the person skilled in the art, as described, for example, in Dr.-Ing. Helmut Jörder, "nonwovens textiles (nonwovens)", avr textbook, P. Keppler Verlag KG, Heusenstamm 1977, pages 13 to 20 are described.
  • the production of corresponding spunbonded nonwovens preferably takes place by processes as described in EP 0 814 188.
  • the basis weight of the nonwoven fabric used for coloring may vary over a wide range.
  • the basis weight of the nonwoven fabric is preferably from 15 to 400 g / m 2 , particularly preferably from 50 to 350 g / m 2 and very particularly preferably from 80 to 200 g / m 2 .
  • a preparation of microfibers or microfilaments containing at least one polyester component and at least one polyamide component and optionally at least one polyurethane component is likewise described in EP 0 814 188, the preparation preferably being carried out by this process.
  • the nonwoven fabric used for coloring consists of unpartified and / or at least partially split microfibers and / or microfilaments of at least one polyester component and at least one polyamide component, these two components preferably in a quantitative ratio of 5 to 95% by weight.
  • % of at least one polyester component and 95 to 5% by weight at least one polyamide component particularly preferably from 15 to 85% by weight of at least one polyester component and from 85 to 15% by weight of at least one polyamide component and very particularly preferably from 30 to 70% by weight of at least one polyester component and from 70 to 30% by weight at least one polyamide component is present.
  • the titre of the microfibers and / or microfilaments present in the nonwoven fabric is preferably ⁇ 1 dtex, particularly preferably 0.02 to 0.95 dtex, very particularly preferably 0.05 to 0.85 dtex and most preferably 0.1 to 0, 5 dtex.
  • the polyamide component of the nonwoven fabric is preferably polyamide 6, polyamide 66 or polyamide 11.
  • the polyester component of the nonwoven fabric preferably consists of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polylactic acid, mixtures thereof or copolyesters.
  • Corresponding copolyesters can be obtained either by partial replacement of the acid component and / or the diol component in the preparation of the polyester, such as in Büttner "basic modified polyester fibers" in "The Applied Macromolecular Chemistry” 40/41, 1974, pages 57 70 (No. 593) or GG Kulkarni, Colourage, 21 August 1986, pages 30 to 33.
  • the corresponding literature descriptions are hereby incorporated by reference and are considered part of the disclosure. If the polyester component is a polyester based on lactic acid, its preparation is described in EP 1 091 028.
  • the azo dye is formed on the nonwoven fabric by coupling at least one dye developer component with at least one fast dye salt or at least one true dye base, after its diazotization, as described below.
  • Another object of the present invention is a process for dyeing and / or printing the nonwoven fabric described above by treating this nonwoven fabric with at least one dye developer component at a temperature of ⁇ 90 ° C and at least one Bachfärbesalz or at least one Mattfärbebase and the dye developer component with the vomfärbesalz or the Mattfärbebase, after the diazotization, is coupled on the nonwoven fabric.
  • the dye developer component and the fast dye salt or fast dye base may be applied to the nonwoven fabric either simultaneously or sequentially. Preferably, these components are applied successively to the nonwoven fabric.
  • a fast dye base is used for coupling with the dye developer component, it must be diazotized prior to coupling, i. be converted into their corresponding diazonium salt.
  • This diazotization can be carried out by customary methods known to the person skilled in the art. Preferably, it is carried out by reacting the respective true base with an inorganic nitrite, preferably sodium nitrite, in the presence of an organic or inorganic acid, preferably hydrochloric acid.
  • a fast dyeing salt is particularly preferably used in the process according to the invention since diazotization prior to coupling is not required here.
  • the dye developer component may preferably be selected from the group consisting of arylamides of aromatic hydroxycarboxylic acids, arylamides of keto acids and hydroxynaphthyl ketones.
  • Preferred arylamides of aromatic hydroxycarboxylic acids are amides of 2-hydroxy-3-naphthoic acid, more preferably 2-hydroxy-3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid o-toluidide, 2-hydroxy-3-naphthoic acid 4, 6-dimethoxy-3-chloroanilide, 2-hydroxy-3-naphthoic acid a-naphthylamide, [bis-2-hydroxy-3-naphthoic acid] dianiside, amides of anthracene, particularly preferably 2-hydroxy-3-anthracene-carboxylic acid o-toluidide, amides of carbazole, more preferably 2-hydroxycarbazole-3-carboxylic acid -4'-choranilide or amides of diphenylene oxide, more preferably 3-hydroxy-2-diphenyl-2-carboxylic acid 2 ', 5'-dimethoxy-
  • the arylamide of a keto acid is preferably diacetacetic acid o-toluidide or terephthaloyl bisacetic acid bis [2-methoxy-4-chloro-5-methyl-anilide.
  • Preferred fastness bases can be selected from the group consisting of o-chloroaniline, o-nitroaniline, m-nitro-p-toluidine, 4-diethylsulfamido-1-amino-1-methoxy-benzene, 4-chloro-2-amino-diphenyl ether, ⁇ -aminoanthraquinone, 4-amino-3-methoxy-azabenzene, 4-amino-1-benzoylamino-3-methoxy-6-methylbenzene, o-dianisidine, 4-amino-4'-methoxy-diphenylamine, 3.5 Bis-trifluoromethylaniline and 3-fluorosulfonylaniline.
  • the nonwoven fabric used for coloring is treated with at least one dye developer component according to the exhaust process, optionally with the addition of carriers.
  • both the treatment temperature and the duration of treatment can vary over a wide range.
  • the treatment temperature is 90 to 150 ° C, more preferably 100 to 130 ° C.
  • the treatment time is preferably 10 to 180 minutes, more preferably 20 to 120 minutes, and most preferably 25 to 60 minutes.
  • the nonwoven fabric used for coloring is treated with at least one dye developer component according to the padding process, to which optionally an intermediate drying is carried out can connect.
  • the duration of the intermediate drying is preferably 30 seconds to 10 minutes, more preferably 2 to 5 minutes.
  • the temperature in the intermediate drying is preferably 80 to 180 ° C, particularly preferably 100 to 150 ° C.
  • the intermediate drying may preferably be followed by a heat treatment, optionally in the presence of steam. The temperature and duration of the heat treatment can vary over a wide range.
  • the temperature in the heat treatment in the presence of water vapor is preferably 100 to 130 ° C, particularly preferably 102 to 120 ° C. If the treatment is carried out without steam, the treatment temperature is preferably 150 to 240 ° C, particularly preferably 175 to 210 ° C.
  • the duration of the heat treatment is preferably 15 seconds to 60 minutes, more preferably 2 to 45 minutes, and most preferably 5 to 30 minutes.
  • the dye developer component, vomerfärbebasen and vomerbrasalze are each used in the form of an aqueous solution.
  • the subsequent coupling of these components to an azo dye on the nonwoven fabric is also preferably carried out in aqueous solution.
  • the treatment of the nonwoven fabric with at least one vomfärbesalz or at least one vomfärbebase and the coupling of the dye developer component with the vomfärbesalz or Echtfetzbebase, after the diazotization, on the nonwoven fabric may also preferably by the exhaust or the padding process, optionally with intermediate drying and optionally subsequent heat treatment, if necessary in the presence of water vapor, wherein both the treatment time and the treatment temperature may vary depending on the particular method.
  • the temperature is preferably -10 to 130 ° C, more preferably 0 to 60 ° C and most preferably 5 to 30 ° C.
  • the treatment time in the exhaustion process is preferably 5 to 120 minutes, more preferably 10 to 60 minutes and most preferably 15 to 45 minutes.
  • the temperature is preferably -10 to 60 ° C, particularly preferably 0 to 30 ° C.
  • the treatment time in the padding process is usually very short and is preferably not more than 10 seconds.
  • nonwoven fabric is printed with one or more of the abovementioned development dyes, this can be done by customary printing processes known to the person skilled in the art.
  • the dye developer component is preferably first applied to the nonwoven fabric by one of the above-mentioned dyeing methods or printed by means of a customary process known to the person skilled in the art.
  • the respective Echtfärbebase or Echtfärbesalz optionally using a template to produce a pattern on the nonwoven fabric is printed.
  • the printing of the nonwoven fabric according to a direct printing method, preferably according to a film printing method, more preferably according to the rotary film or flat film printing method, or according to the ink-jet method.
  • the printing of the nonwoven fabric may preferably be followed by intermediate drying and, if appropriate, subsequent heat treatment, if appropriate in the presence of steam, which in each case may preferably be carried out under the conditions indicated above.
  • the printing of the described nonwoven fabric using printing pastes can be prepared by conventional methods known in the art and in addition to the respective dye developer component or Echtfärbebase or Echtfärbesalzes also contain other conventional auxiliaries, which can be preferably selected from the group from thickeners, crosslinkers, plasticizers, defoamers, wetting agents and moisture promoters. Furthermore, it is also possible from the Echtfärbebase to generate the corresponding diazonium salt in the printing paste by diazotization.
  • the printing pastes contain, in addition to the respective dye developer component or the Echtfärbebase or Echtfärbesalzes as another ingredient only one or more thickening agents, which can be preferably selected from the group of natural or synthetic thickeners.
  • Natural thickeners may preferably be selected from the group comprising optionally partially degraded starch, vegetable gums, locust bean gum, etherified polysaccharides and alginates.
  • Synthetic thickeners may preferably be selected from the group of water-soluble carboxyl group-containing polymers, which may preferably consist of (meth) acrylic acid and / or maleic acid hydride.
  • the coupling of the components to the azo dye can be followed by aftertreatment of the nonwoven fabric by heating or treatment with water vapor, even at elevated temperature.
  • the treatment with steam - the post-fuming - is preferably carried out at a temperature of 100 to 130 ° C, preferably at 102 to 120 ° C, the heating (post-fixing) at a temperature of 150 to 240 ° C, preferably at 175 to 210 ° C.
  • the duration of the treatment may in each case preferably be 10 seconds to 30 minutes, particularly preferably 30 seconds to 15 minutes, very particularly preferably 2 minutes to 10 minutes.
  • the dyeing and / or printing of the nonwoven fabric may be followed by a cleaning of the nonwoven fabric, preferably by rinsing with water or an aqueous solution containing sodium hydrosulfite and sodium hydroxide, even at elevated temperature, and / or optionally soaps the nonwoven fabric, the conditions of course so too choose that the applied azo dye is not completely destroyed again.
  • a treatment of the dyed and / or printed nonwoven fabric with a color-intensifying aid can be carried out after dyeing and / or printing in the course of the finishing.
  • color-intensifying agents all chemicals are considered which can measure the refraction angle of the light on the surface of the nonwoven fabric, e.g. by forming a film, so that the calculation index between the air and the nonwoven fabric has a value greater than 1.
  • Suitable chemicals are, for example, polyacrylates, polyurethanes and polysiloxanes which are commercially available, for example, under the name Badena® Eco 282, Finistrol® KSE-D, Baypret® USV and Arristan® 64. If the film formed consists of chemicals which protect the dyes also against external influences, such. Badena® Eco 282, at the same time an improvement in color fastness can be achieved.
  • the color-intensifying aid can be applied by customary methods known to the person skilled in the art.
  • the color-intensifying aid may preferably be applied to the textile material at a pH of from 2 to 12, preferably from 3 to 9, particularly preferably from 4 to 8, using the padding process and at temperatures of from 40 to 180 ° C., preferably from 100 to 160 ° C for a period of 1 second to 120 minutes, preferably from 5 seconds to 45 minutes, more preferably from 30 Seconds can be fixed up to 2 minutes.
  • the particular amount of color-enhancing agent that is suitable can vary and can be determined by the person skilled in the art by simple preliminary tests. For Badena® Eco 282, the suitable amount is preferably 10 to 100 g / l of liquor, more preferably 20 to 50 g / l of liquor.
  • the printed and / or dyed nonwoven fabric according to the invention made of unsplit and / or at least partially split microfibers and / or microfilaments of synthetic polymers comprising at least one polyester component and at least one polyamide component and optionally at least one polyurethane component is characterized by good to very good color fastness, even after heat treatment, in particular by good to very good washing, welding, water and light fastness and good rubbing fastness.
  • the nonwoven fabric dyed and / or printed by the method according to the invention is therefore particularly suitable for the production of clothing, home textiles, linings, preferably for luggage, as well as for the production of textile products in the field of medicine and / or hygiene.
  • Another object of the present invention is therefore the use of at least one dyed and / or printed nonwoven fabric according to the invention for the production of clothing, as home textiles, as lining materials, preferably linings for luggage, such as e.g. Suitcases or bags, as well as textile material in the field of medicine and / or hygiene.
  • the lightfastness of the dyed and / or printed synthetic textile material according to the invention was, according to EN ISO 105 B02, the wash fastness at 40 ° C, even after heat treatment, according to EN ISO 105 C06 A2S, the resistance to water according to EN ISO 104 E01, the resistance to Welding according to EN ISO 104 E04 and resistance to mechanical rubbing in accordance with EN ISO 105 X12.
  • a spunbonded nonwoven having a weight per unit area of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of nylon 66 having a titre of about 0.15 dtex was extracted by means of an aqueous hydroxynaphthoic acid Primer formulation containing CI Azoic Coupling Component 5 (trade name: Naphtol AS-G, DyStar) and then blended with a true color salt preparation containing CI Azoic Diazo Component 33 (Salt) (trade name: fast-release salt FRN, DyStar), coupled.
  • the naphthol was first dissolved by means of cold dissolving method, with 1.4 g of naphthol with 10 ml of a 10 wt .-% - castor oil solution and 5 ml of a 10 wt .-% - sodium hydroxide solution pasted in with 20 ml of 60 ° C warm water containing 0.0175 g of a complexing agent based on trisodium nitrilotriacetate, were poured over.
  • 10 g of the spun-bonded nonwoven fabric were then primed with the solution thus obtained at a liquor ratio of 1:20.
  • the solution was placed together with the nonwoven fabric in a dyeing cup and heated to 130 ° C at 1.5 ° C / min. After a residence time of 30 min at 130 ° C was cooled at 1.5 ° C / min to 80 ° C and 10 min at a liquor ratio of 1:10 with 199.8 ml of 40 ° C warm water containing 0.2 ml a 32 wt .-% sodium hydroxide solution, 10 g of sodium chloride and 0.1 g of a complexing agent based on trisodium nitrilotriacetat, rinsed.
  • the napthol-primed nonwoven fabric was treated in a dyeing machine with this solution at 20 ° C for 30 min and then for 15 min at 70 ° C with a solution containing 1 g / l of sodium carbonate and 0.5 g / l of a dispersant based on an ethoxylated higher alcohol, soaped.
  • a spunbonded nonwoven having a basis weight of 100 g / m 2 consisting of partially split microfibers of 70 wt .-% polyethylene terephthalate and 30 wt .-% polyamide 66 with a titer of about 0.15 dtex was primed and rinsed analogously to Example 1 ,
  • Example 1 Development with the true color salt preparation according to Example 1 was carried out immediately after priming in the padding process. To this was dissolved 6.92 g of the true color salt preparation with 99 ml of 15 ° C. warm water containing 1 ml of a 7% strength by weight solution of a dispersant based on an ethoxylated higher alcohol and 1 g of sodium acetate. The pH was adjusted to 5 with 60% strength by weight acetic acid. This solution was padded at 20 ° C on the primed, wet nonwoven fabric. The liquor pickup was 100 wt .-%, based on the weight of the nonwoven fabric used. Subsequently, the nonwoven fabric was treated at 20 ° C for 60 seconds with circulating air and soaped as indicated in Example 1.
  • a spunbonded nonwoven fabric having a weight per unit area of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 having a titer of about 0.15 dtex was prepared by exhaustion with a liquid hydroxybenzocarbazolecarboxylic acid.
  • the primer was carried out by exhaustion at a liquor ratio of 1:20.
  • the naphtol-primed nonwoven fabric was treated in a dyeing machine with this solution at 20 ° C for 30 minutes and then for 15 minutes at 70 ° C with a solution containing 1 g / l of sodium carbonate and 0.5 g / l of a dispersant based on an ethoxylated higher alcohol contained, soaped.
  • a spunbonded nonwoven fabric having a weight per unit area of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 having a titer of about 0.15 dtex was treated in the padding process with a liquid hydroxybenzocarbazolecarboxylic acid.
  • the primed goods were padded with this solution at 20 ° C -
  • the liquor pickup was 100 wt .-%, based on the eincuten nonwoven fabric, then 60 seconds was treated with circulating air at 20 ° C, post-fixed at 200 ° C for 180 seconds and as soaped in Example 1.
  • a spunbonded nonwoven having a basis weight of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 having a titer of about 0.15 dtex was first treated with Naphtol AS (Dystar). , an aqueous hydroxynaphthoic acid preparation containing CI Azoid Coupling Component 2, as a dye developer component padded. Subsequently, the nonwoven fabric was dried at 140 ° C for 90 seconds.
  • a stock paste A was prepared from 500 g of Diagum A8 (BF Goodrich, Diamalt, Barcelona, Spain), a locust bean thickener, 491 g of water and 9 g of sodium nitrite, and a stock paste B of 500 g of Diagum A8, 440 g of water and 60 g g phosphoric acid produced.
  • a printing paste 30 g of Echtbase Echtrot B (Dystar), C.I. Azoic Diazo Component 5 diluted with 70 g of water, stirred into 600 g of stock paste A and admixed with 300 g of stock paste B.
  • the paste thus obtained was then stirred for 5 minutes, so that a diazotization of the true base was carried out.
  • the thus-obtained paste was then screen-printed on the nonwoven fabric previously padded with the dye developer component using a stencil.
  • To remove the uncoupled Echtbase the nonwoven fabric was then treated for 30 minutes at a temperature of 90 ° C with sodium dithionite in aqueous sodium hydroxide solution and then soaped with Calgon T and soda.
  • a spunbonded nonwoven having a weight per unit area of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 having a titer of about 0.15 dtex was initially treated with an aqueous solution of naphthol AS (Dystar), a hydroxynaphthoic acid preparation containing CI Azoic Coupling Component 2, padded as a dye developer component. Subsequently, the nonwoven fabric was dried at 140 ° C for 90 seconds.
  • the thus pretreated nonwoven fabric was prepared by using a stencil with a paste of 200 g of aluminum sulfate monohydrate, 200 g of water and 600 g Printed cellulose ether and then dried for 3 minutes at a temperature of 120 ° C.
  • the nonwoven fabric was then reductively cleaned by means of sodium hydrosulfite and sodium hydroxide solution, rinsed with hot running water and then boiled with a solution containing 1 g / l Naphtopon E (Bayer AG, Germany), Calgon T (Benkieser) and soda.
  • a spunbonded nonwoven having a weight per unit area of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 having a titer of about 0.15 dtex was initially treated with an aqueous solution of naphthol AS (Dystar), a hydroxynaphthoic acid preparation containing CI Azoic Coupling Component 2, padded as a dye developer component. Subsequently, the nonwoven fabric was dried at 140 ° C for 90 seconds.
  • the thus pretreated was printed with a paste of 60 g Echtorgangesalz GGD, 3 g of the dispersant Dispersogen ASN, 317 g of water, 70 g of aluminum sulfate monohydrate, 550 g Tylose H 300 and then dried for 3 minutes at a temperature of 120 ° C. ,
  • the nonwoven fabric was then reductively cleaned with the aid of sodium hydrosulfite and sodium hydroxide solution, rinsed with hot flowing water and then boiled with a solution containing 1 g / l Naphtopon E (Bayer AG), Calgon T (Benkieser) and soda.
  • Table 1 ⁇ / b>
  • Example 1 Color: yellow
  • Example 2 Color: yellow
  • Example 3 Color: greyish brown

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Description

Die vorliegende Erfindung betrifft einen gefärbten und/oder bedruckten Vliesstoff aus ungesplitteten und/oder zumindest teilweise gesplitteten Mikrofasern und/oder Mikrofilamenten aus synthetischen Polymeren enthaltend wenigstens eine Polyesterkomponente und wenigstens eine Polyamidkomponente und gegebenenfalls wenigstens eine Polyurethankomponente, der mit wenigstens einem auf dem Vliesstoff erzeugten Azofarbstoff gefärbt und/oder bedruckt worden ist sowie ein Verfahren zu dessen Färbung und/oder Bedruckung.The present invention relates to a dyed and / or printed nonwoven fabric made of unsplit and / or at least partially split microfibers and / or microfilaments of synthetic polymers containing at least one polyester component and at least one polyamide component and optionally at least one polyurethane component comprising at least one azo dye formed on the nonwoven fabric dyed and / or printed and a method for its coloring and / or printing.

Aus Kunststoffen hergestellte textile Materialien können mit herkömmlichen Textilfärbe- oder Textildruckverfahren häufig nur in unzureichender Qualität gefärbt oder bedruckt werden. Schwierigkeiten beim Färben oder Bedrucken ergeben sich insbesondere dann, wenn das textile Material verschiedene Kunststoffkomponenten, beispielsweise Polyester und Polyamid, umfaßt, da diese üblicherweise ein stark unterschiedliches Färbeverhalten zeigen, wie beispielsweise aus BASF "Manual-Dying and Finishing of Polyamide Fibres and their Blends with other fibres" B358e /12.72, Seite 149 hervorgeht.Fabric made of plastics textile materials can often be dyed or printed with conventional textile dyeing or textile printing process often in insufficient quality. Difficulties in dyeing or printing arise in particular when the textile material comprises various plastic components, such as polyester and polyamide, since these usually show a very different dyeing behavior, such as BASF "Manual-Dying and Finishing of Polyamide Fibers and their blends with other fibers "B358e / 12.72, page 149.

Wird z.B. der Polyesteranteil eines solchen textilen Materials mit einem Dispersionsfarbstoff gefärbt, kommt es häufig vor, daß der Polyamidanteil des Materials durch diesen Farbstoff angeschmutzt wird und/oder der Farbstoff unter Hitzeeinwirkung von der Polyesterkomponente auf die Polyamidkomponente migriert. Hieraus resultieren mangelnde Farbechtheiten und eine unzureichende Egalität des gefärbten textilen Materials. Eine entsprechende Problematik ist auch bei anderen Kunstoffkomponenten, wie beispielsweise Polyurethan, zu beobachten.For example, if the polyester content of such a textile material dyed with a disperse dye, it often happens that the polyamide portion of the material is soiled by this dye and / or the dye under heat from the polyester component on the Polyamide component migrated. This results in lack of color fastness and inadequate levelness of the dyed textile material. A corresponding problem is also observed with other plastic components, such as polyurethane.

Die Färbung von textilen Materialien, die aus einer Mischung von Polyester- und Polyamid Mikrofasern bestehen, bereitet noch größere Schwierigkeiten, wie z.B. in "Färben von Polyester-, Polyester-/Polyamid- und Polyacrylnitril-Mikrofasern" - Technische Information 00127.00.94, Sandoz Chemikalien AG, Geschäftsbereich Textil, 4132 Muttenz, Seiten 24 bis 40 ausgeführt wird.
Zum Färben und/oder Bedrucken von textilen Materialien, die verschiedene Kunststoffkomponenten enthalten, werden daher im allgemeinen mehrstufige Färbe- bzw. Druckverfahren eingesetzt, wobei in jeder Stufe dieser Verfahren jeweils eine der Kunststoffkomponenten mit einer für sie geeigneten Farbstoffklasse gefärbt und/oder bedruckt wird. Zwischen den verschiedenen Färbestufen sind häufig relativ aufwendige Reinigungsschritte erforderlich, um u.a. überschüssigen Farbstoff oder unecht auf dem Material gebundenen Farbstoff zu entfernen.The dyeing of textile materials consisting of a mixture of polyester and polyamide microfibers causes even greater difficulties, as in "Dyeing of polyester, polyester / polyamide and polyacrylonitrile microfibers" - Technical Information 00127.00.94, Sandoz Chemikalien AG, Textile Division, 4132 Muttenz, pages 24 to 40 is executed.
For dyeing and / or printing textile materials containing various plastic components, multistage dyeing or printing processes are therefore generally used, wherein in each stage of these processes one of each of the plastic components is dyed and / or printed with a dye class suitable for it. Between the different dyeing stages relatively expensive cleaning steps are often required to remove, inter alia, excess dye or improperly bound to the material dye.

Besonders problematisch ist das Färben oder Bedrucken von Vliesstoffen, die aus einem Gemisch von Mikrofasern und/oder Mikrofilamenten bestehen, wie beispielsweise Polyester/Polyamid-Splittfasern, da die Splittfasern im Vliesstoff unregelmäßig verteilt sind, während in entsprechenden Polyamid/Polyester-Mikrofasergeweben dagegen üblicherweise nur eine Komponente, im allgemeinen der Schuß, aus Polyamid/Polyester-Splittfasern besteht.Particularly problematic is the dyeing or printing of nonwovens, which consist of a mixture of microfibers and / or microfilaments, such as polyester / polyamide split fibers, since the split fibers are distributed irregularly in the nonwoven, while in corresponding polyamide / polyester microfiber fabrics, however, usually only a component, generally the weft, consists of polyamide / polyester chippings.

Des weiteren ist bei derartigen Vliesstoffen die Dichte der Fasern und/oder Filamente, d.h. die Zahl der Fasern und/oder Filamente pro Flächeneinheit, höher als bei entsprechenden Geweben oder Gewirken, so daß zur Färbung solcher Vliesstoffe erhöhte Farbstoffmengen erforderlich sind. Dieser erhöhte Farbstoffeinsatz einerseits und die ungleichmäßige Verteilung der Fasern andererseits führen dazu, daß aus mehreren Kunststoffkomponenten hergestellte, gefärbte oder bedruckte Vliesstoffe aus Mikrofasern und/oder Mikrofilamenten im allgemeinen schlechtere Farbechtheiten aufweisen als entsprechende Gewebe aus den selben synthetischen Polymeren.Furthermore, in such nonwoven fabrics, the density of the fibers and / or filaments, ie the number of fibers and / or filaments per unit area, higher than corresponding fabrics or knitted fabrics, so that for dyeing Such nonwovens require increased amounts of dye. This increased use of dye on the one hand and the uneven distribution of the fibers on the other hand cause that made of several plastic components, dyed or printed nonwoven fabrics of microfibers and / or microfilaments in general have worse color fastness than corresponding fabrics of the same synthetic polymers.

Aus GB 1 437 204 ist ein Verfahren zum Färben und Bedrucken von organischem Material unter Verwendung von Entwicklungsfarbstoffen bekannt.From GB 1 437 204 a process for dyeing and printing organic material using developing dyes is known.

Die DE-OS-25 13 533 beschreibt ein Verfahren zum Bedrucken und Klotzfärben von Mischgewebe.DE-OS-25 13 533 describes a process for printing and pad dyeing blended fabric.

Der US 3,081,141 ist ein Färbeverfahren für Gewebe und Vliesstoffe zu entnehmen, in dem zunächst die Farbstoffkomponenten separat auf das zu färbende Substrat aufgetragen werden und anschließend der Farbstoff in situ auf dem Substrat erzeugt wird.US Pat. No. 3,081,141 discloses a dyeing process for fabrics and nonwovens, in which first the dye components are applied separately to the substrate to be dyed and subsequently the dye is produced in situ on the substrate.

Die Aufgabe der vorliegenden Erfindung bestand daher darin, eine geeignete Farbstoffklasse auszuwählen, die das Färben und/oder Bedrucken solcher Vliesstoffe aus verschiedenen Kunststoffkomponenten mit nur einer Farbstoffklasse ermöglicht und damit einen gefärbten und/oder bedruckten Vliesstoff aus ungesplitteten und/oder zumindest teilweise gesplitteten Mikrofasern und/oder Mikrofilamenten aus synthetischen Polymeren enthaltend wenigstens eine Polyesterkomponente und wenigstens eine Polyamidkomponente und gegebenenfalls wenigstens eine Polyurethankomponente zur Verfügung zu stellen, der sich durch gute bis sehr gute Farbechtheiten, insbesondere Wasch-, Schweiß-, Wasser- und Licht- sowie durch gute Reibechtheiten auszeichnet.The object of the present invention was therefore to select a suitable class of dyes, which allows the dyeing and / or printing of such nonwoven fabrics of different plastic components with only one class of dyes and thus a dyed and / or printed nonwoven fabric of ungrounded and / or at least partially split microfibers and / or microfilaments of synthetic polymers containing at least one polyester component and at least one polyamide component and optionally at least one polyurethane component to provide, which is characterized by good to very good color fastness, especially washing, welding, water and light and good rub fastness ,

Diese Aufgabe wurde durch die Bereitstellung eines gefärbten und/oder bedruckten Vliesstoffes aus ungesplitteten und/oder zumindest teilweise gesplitteten Mikrofasern und/oder Mikrofilamenten aus synthetischen Polymeren enthaltend wenigstens eine Polyesterkomponente und wenigstens eine Polyamidkomponente und gegebenenfalls wenigstens eine Polyurethankomponente gelöst, der mit wenigstens einem auf dem Vliesstoff erzeugten Azofarbstoff, einem sogenannten Entwicklungsfarbstoff, gefärbt und/oder bedruckt worden ist.This object has been achieved by the provision of a dyed and / or printed nonwoven fabric made of unsplit and / or at least partially split microfibers and / or microfilaments of synthetic polymers containing at least one polyester component and at least one polyamide component and optionally at least one polyurethane component having at least one on the Nonwoven produced azo dye, a so-called development dye, dyed and / or printed.

Der zum Einsatz kommende Vliesstoff ist ein Stapelfaservliesstoff oder ein Spinnvliesstoff, vorzugsweise eine Spinnvliesstoff, aus ungesplitteten und/oder zumindest teilweise gesplitteten Mikrofasern und/oder Mikrofilamenten. Die Herstellung entsprechender Vliesstoffe kann nach üblichen, dem Fachmann bekannten Verfahren erfolgen, wie sie beispielsweise in Dr. Helmut Jörder, "Textilien auf Vliesbasis (Nonwovens)", avr-Fachbuch, P. Keppler Verlag KG, Heusenstamm 1977, Seiten 13 bis 20 beschrieben sind. Die Herstellung entsprechender Spinnvliesstoffe erfolgt bevorzugt nach Verfahren, wie sie in der EP 0 814 188 beschrieben werden.The nonwoven used is a staple fiber nonwoven or a spunbonded nonwoven, preferably a spunbond nonwoven, of un-split and / or at least partially split microfibers and / or microfilaments. The production of corresponding nonwovens can be carried out by customary methods known to the person skilled in the art, as described, for example, in Dr.-Ing. Helmut Jörder, "nonwovens textiles (nonwovens)", avr textbook, P. Keppler Verlag KG, Heusenstamm 1977, pages 13 to 20 are described. The production of corresponding spunbonded nonwovens preferably takes place by processes as described in EP 0 814 188.

Das Flächengewicht des zur Farbgebung eingesetzten Vliesstoffs kann über einen breiten Bereich variieren. Vorzugsweise beträgt das Flächengewicht des Vliesstoffs 15 bis 400 g/m2, besonders bevorzugt 50 bis 350 g/m2 und ganz besonders bevorzugt 80 bis 200 g/m2.The basis weight of the nonwoven fabric used for coloring may vary over a wide range. The basis weight of the nonwoven fabric is preferably from 15 to 400 g / m 2 , particularly preferably from 50 to 350 g / m 2 and very particularly preferably from 80 to 200 g / m 2 .

Eine Herstellung von Mikrofasern bzw. Mikrofilamenten enthaltend wenigstens eine Polyesterkomponente und wenigstens eine Polyamidkomponente und gegebenenfalls wenigstens eine Polyurethankomponente ist ebenfalls in der EP 0 814 188 beschrieben, wobei die Herstellung bevorzugt nach diesem Verfahren erfolgt.A preparation of microfibers or microfilaments containing at least one polyester component and at least one polyamide component and optionally at least one polyurethane component is likewise described in EP 0 814 188, the preparation preferably being carried out by this process.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung besteht der zur Farbgebung eingesetzte Vliesstoff aus ungesplitteten und/oder zumindest teilweise gesplitteten Mikrofasern und/oder Mikrofilamenten aus wenigstens einer Polyesterkomponente und wenigstens einer Polyamidkomponente, wobei diese beiden Komponenten bevorzugt in einem Mengenverhältnis von 5 bis 95 Gew.-% wenigstens einer Polyesterkomponente und 95 bis 5 Gew.-% wenigstens einer Polyamidkomponente, besonders bevorzugt aus 15 bis 85 Gew.-% wenigstens einer Polyesterkomponente und 85 bis 15 Gew-% wenigstens einer Polyamidkomponente und ganz besonders bevorzugt aus 30 bis 70 Gew.-% wenigstens einer Polyesterkomponente und 70 bis 30 Gew.-% wenigstens einer Polyamidkomponente vorliegen.In a preferred embodiment of the present invention, the nonwoven fabric used for coloring consists of unpartified and / or at least partially split microfibers and / or microfilaments of at least one polyester component and at least one polyamide component, these two components preferably in a quantitative ratio of 5 to 95% by weight. % of at least one polyester component and 95 to 5% by weight at least one polyamide component, particularly preferably from 15 to 85% by weight of at least one polyester component and from 85 to 15% by weight of at least one polyamide component and very particularly preferably from 30 to 70% by weight of at least one polyester component and from 70 to 30% by weight at least one polyamide component is present.

Vorzugsweise beträgt der Titer der in dem Vliesstoff vorliegenden Mikrofasern und/oder Mikrofilamente ≤ 1 dtex, besonders bevorzugt 0,02 bis 0,95 dtex, ganz besonders bevorzugt 0,05 bis 0,85 dtex und am meisten bevorzugt 0,1 bis 0,5 dtex.The titre of the microfibers and / or microfilaments present in the nonwoven fabric is preferably ≦ 1 dtex, particularly preferably 0.02 to 0.95 dtex, very particularly preferably 0.05 to 0.85 dtex and most preferably 0.1 to 0, 5 dtex.

Die Polyamidkomponente des Vliesstoffs ist bevorzugt Polyamid 6, Polyamid 66 oder Polyamid 11.The polyamide component of the nonwoven fabric is preferably polyamide 6, polyamide 66 or polyamide 11.

Die Polyesterkomponente des Vliesstoffs besteht vorzugsweise aus Polyethylenterephthalat, Polypropylenterephthalat, Polybutylenterephthalat, Polymilchsäure, deren Mischungen oder Copolyestern.The polyester component of the nonwoven fabric preferably consists of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polylactic acid, mixtures thereof or copolyesters.

Entsprechende Copolyester lassen sich entweder durch teilweisen Austausch der Säure-Komponente und/oder der Diol-Komponente bei der Herstellung des Polyesters erhalten, wie beispielsweise in Büttner "Basisch modifizierte Polyesterfasern" in "Die Angewandte Makromolekulare Chemie" 40/41, 1974, Seiten 57-70 (Nr. 593) oder G.G. Kulkarni, Colourage, 21. August 1986, Seiten 30 bis 33 beschrieben. Die entsprechenden Literaturbeschreibungen werden hiermit als Referenz eingeführt und gelten als Teil der Offenbarung. Sofern die Polyesterkomponente ein Polyester auf Basis von Milchsäure ist, wird dessen Herstellung in der EP 1 091 028 beschrieben.Corresponding copolyesters can be obtained either by partial replacement of the acid component and / or the diol component in the preparation of the polyester, such as in Büttner "basic modified polyester fibers" in "The Applied Macromolecular Chemistry" 40/41, 1974, pages 57 70 (No. 593) or GG Kulkarni, Colourage, 21 August 1986, pages 30 to 33. The corresponding literature descriptions are hereby incorporated by reference and are considered part of the disclosure. If the polyester component is a polyester based on lactic acid, its preparation is described in EP 1 091 028.

Der Azofarbstoff wird auf dem Vliesstoff durch Kupplung wenigstens einer Farbstoffentwicklerkomponente mit wenigstens einem Echtfärbesalz oder wenigstens einer Echtfärbebase, nach deren Diazotierung, erzeugt, wie untenstehend beschrieben wird.The azo dye is formed on the nonwoven fabric by coupling at least one dye developer component with at least one fast dye salt or at least one true dye base, after its diazotization, as described below.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Färben und/oder Bedrucken des vorstehend beschriebenen Vliesstoffes, indem dieser Vliesstoff mit wenigstens einer Farbstoffentwicklerkomponente bei einer Temperatur von ≥ 90 °C und wenigstens einem Echtfärbesalz oder wenigstens einer Echtfärbebase behandelt und die Farbstoffentwicklerkomponente mit dem Echtfärbesalz oder der Echtfärbebase, nach deren Diazotierung, auf dem Vliesstoff gekuppelt wird.Another object of the present invention is a process for dyeing and / or printing the nonwoven fabric described above by treating this nonwoven fabric with at least one dye developer component at a temperature of ≥ 90 ° C and at least one Echtfärbesalz or at least one Echtfärbebase and the dye developer component with the Echtfärbesalz or the Echtfärbebase, after the diazotization, is coupled on the nonwoven fabric.

Entsprechende Farbstoffentwicklerkomponenten, Echtfärbebasen und Echtfärbesalze, die sich zur Herstellung eines Azofarbstoffes durch Kupplung auf dem zu färbenden Vliesstoff eignen, sind dem Fachmann an sich bekannt und beispielsweise in "Rath-Lehrbuch der Textilchemie, Springer Verlag Berlin, Heidelberg, New York, 3. Auflage 1972, Seiten 422 bis 432, Seiten 548 bis 556 und Seiten 690 bis 697 oder aus den entsprechenden Farbstoffkarten der jeweiligen Farbstoffhersteller, z.B. "Naphtol® AS, Echtfärbebasen/Echtfärbesalze DF1007 D/E" von der Firma DyStar Textilfarben, Frankfurt beschrieben. Die jeweils geeigneten Mengen der einzusetzenden Komponenten, d.h. der Farbstoffentwicklerkomponenten, Echtfärbebasen und Echtfärbesalze können variieren, beispielsweise in Abhängigkeit von dem Titer der Mikrofasern und/oder Mikrofilamente oder der eingesetzten Polymerkomponenten. Sie können vom Fachmann durch Vorversuche ermittelt werden.Corresponding dye developer components, Echtfärbebasen and Echtfärbesalze that are suitable for the preparation of an azo dye by coupling on the nonwoven to be dyed are known in the art and known for example in "Rath textbook of textile chemistry, Springer Verlag Berlin, Heidelberg, New York, 3rd edition 1972, pages 422 to 432, pages 548 to 556 and pages 690 to 697 or from the corresponding dye cards of the respective dye manufacturer, eg "Naphtol® AS, Echtfärbebasen / Echtfärbesalze DF1007 D / E" from DyStar Textile Colors, Frankfurt suitable amounts of the components to be used, ie the dye developer components, fast dye bases and fast dyeing salts, may vary, for example depending on the microfiber and / or microfilament or polymer component used, and can be determined by a person skilled in the art by preliminary experiments.

Die Farbstoffentwicklerkomponente und das Echtfärbesalz oder die Echtfärbebase können entweder gleichzeitig oder nacheinander auf den Vliesstoff aufgebracht werden. Vorzugsweise werden diese Komponenten nacheinander auf den Vliesstoff aufgebracht.The dye developer component and the fast dye salt or fast dye base may be applied to the nonwoven fabric either simultaneously or sequentially. Preferably, these components are applied successively to the nonwoven fabric.

Sofern zur Kupplung mit der Farbstoffentwicklerkomponente eine Echtfärbebase eingesetzt wird, muß diese vor der Kupplung diazotiert, d.h. in ihr entsprechendes Diazoniumsalz übergeführt werden. Diese Diazotierung kann nach üblichen, dem Fachmann bekannten Methoden erfolgen. Vorzugsweise erfolgt sie durch Umsetzung der jeweiligen Echtbase mit einem anorganischen Nitrit, vorzugsweise Natriumnitrit, in Gegenwart einer organischen oder anorganischen Säure, vorzugsweise Salzsäure.If a fast dye base is used for coupling with the dye developer component, it must be diazotized prior to coupling, i. be converted into their corresponding diazonium salt. This diazotization can be carried out by customary methods known to the person skilled in the art. Preferably, it is carried out by reacting the respective true base with an inorganic nitrite, preferably sodium nitrite, in the presence of an organic or inorganic acid, preferably hydrochloric acid.

Besonders bevorzugt kommt in dem erfindungsgemäßen Verfahren daher ein Echtfärbesalz, zum Einsatz, da eine Diazotierung vor der Kupplung hier nicht erforderlich ist.Therefore, a fast dyeing salt is particularly preferably used in the process according to the invention since diazotization prior to coupling is not required here.

Die Farbstoffentwicklerkomponente kann bevorzugt ausgewählt werden aus der Gruppe bestehend aus Arylamiden aromatischer Hydroxycarbonsäuren, Arylamiden von Ketosäuren und Hydroxynaphthylketonen.The dye developer component may preferably be selected from the group consisting of arylamides of aromatic hydroxycarboxylic acids, arylamides of keto acids and hydroxynaphthyl ketones.

Bevorzugt werden als Arylamide aromatischer Hydroxycarbonsäuren Amide der 2-Hydroxy-3-naphthoesäure, besonders bevorzugt 2-Hydroxy-3-naphthoesäure-anilid, 2-Hydroxy-3-naphthoesäure-o-toluidid, 2-Hydroxy-3-naphthoesäure-4,6-dimethoxy-3-chloranilid, 2-Hydroxy-3-naphthoesäure-a-Naphthylamid, [Bis-2-hydroxy-3-naphthoesäure]-dianisid, Amide des Anthracens, besonders bevorzugt 2-Hydroxy-3-anthracen-carbonsäure-o-toluidid, Amide des Carbazols, besonders bevorzugt 2-Hydroxycarbazol-3-carbonsäure -4'-choranilid oder Amide des Diphenylenoxids, besonders bevorzugt 3-Hydroxy-diphenylenoxid-2-carbonsäure-2',5'-dimethoxy-anilid eingesetzt.Preferred arylamides of aromatic hydroxycarboxylic acids are amides of 2-hydroxy-3-naphthoic acid, more preferably 2-hydroxy-3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid o-toluidide, 2-hydroxy-3-naphthoic acid 4, 6-dimethoxy-3-chloroanilide, 2-hydroxy-3-naphthoic acid a-naphthylamide, [bis-2-hydroxy-3-naphthoic acid] dianiside, amides of anthracene, particularly preferably 2-hydroxy-3-anthracene-carboxylic acid o-toluidide, amides of carbazole, more preferably 2-hydroxycarbazole-3-carboxylic acid -4'-choranilide or amides of diphenylene oxide, more preferably 3-hydroxy-2-diphenyl-2-carboxylic acid 2 ', 5'-dimethoxy-anilide used.

Als Arylamid einer Ketosäure wird bevorzugt Diacetessigsäure-o-toluidid oder Terephthaloyl-bis-essigsäure-bis-[2-methoxy-4-chlor-5-methyl-anilid eingesetzt. Bevorzugte Echtfärbebasen können ausgewählt werden aus der Gruppe bestehend aus o-Chloranilin, o-Nitroanilin, m-Nitro-p-toluidin, 4-Diethylsulfamido-1-amino-1-methoxy-benzol, 4-Chlor-2-amino-diphenylether, α-Amino-anthrachinon, 4-Amino-3-Methoxy-azabenzol, 4-Amino-1-benzoylamino-3-methoxy-6-methylbenzol, o-Dianisidin, 4-Amino-4'-methoxy-diphenylamin, 3,5-Bis-trifluormethylanilin und 3-Fluorsulfonylanilin.The arylamide of a keto acid is preferably diacetacetic acid o-toluidide or terephthaloyl bisacetic acid bis [2-methoxy-4-chloro-5-methyl-anilide. Preferred fastness bases can be selected from the group consisting of o-chloroaniline, o-nitroaniline, m-nitro-p-toluidine, 4-diethylsulfamido-1-amino-1-methoxy-benzene, 4-chloro-2-amino-diphenyl ether, α-aminoanthraquinone, 4-amino-3-methoxy-azabenzene, 4-amino-1-benzoylamino-3-methoxy-6-methylbenzene, o-dianisidine, 4-amino-4'-methoxy-diphenylamine, 3.5 Bis-trifluoromethylaniline and 3-fluorosulfonylaniline.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens erfolgt die Behandlung des zur Farbgebung eingesetzten Vliesstoffes mit wenigstens einer Farbstoffentwicklerkomponente gemäß dem Ausziehverfahren, gegebenenfalls unter Zusatz von Carriern. Hierbei können sowohl die Behandlungstemperatur als auch die Behandlungsdauer über einen breiten Bereich variieren.In a preferred embodiment of the process according to the invention, the nonwoven fabric used for coloring is treated with at least one dye developer component according to the exhaust process, optionally with the addition of carriers. Here, both the treatment temperature and the duration of treatment can vary over a wide range.

Vorzugsweise beträgt die Behandlungstemperatur 90 bis 150 °C, besonders bevorzugt 100 bis 130 °C. Die Behandlungsdauer beträgt bevorzugt 10 bis 180 Minuten, besonders bevorzugt 20 bis 120 Minuten und ganz besonders bevorzugt 25 bis 60 Minuten.Preferably, the treatment temperature is 90 to 150 ° C, more preferably 100 to 130 ° C. The treatment time is preferably 10 to 180 minutes, more preferably 20 to 120 minutes, and most preferably 25 to 60 minutes.

In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens erfolgt die Behandlung des zur Farbgebung eingesetzten Vliesstoffes mit wenigstens einer Farbstoffentwicklerkomponente gemäß dem Klotzverfahren, an das sich gegebenenfalls eine Zwischentrocknung anschließen kann. Die Dauer der Zwischentrocknung beträgt vorzugsweise 30 Sekunden bis 10 Minuten, besonders bevorzugt 2 bis 5 Minuten. Die Temperatur bei der Zwischentrocknung beträgt bevorzugt 80 bis 180 °C, besonders bevorzugt 100 bis 150 °C. An die Zwischentrocknung kann sich bevorzugt eine Hitzebehandlung, gegebenenfalls in Gegenwart von Wasserdampf anschließen. Die Temperatur und die Dauer der Hitzebehandlung können über einen breiten Bereich variieren.In a further preferred embodiment of the process according to the invention, the nonwoven fabric used for coloring is treated with at least one dye developer component according to the padding process, to which optionally an intermediate drying is carried out can connect. The duration of the intermediate drying is preferably 30 seconds to 10 minutes, more preferably 2 to 5 minutes. The temperature in the intermediate drying is preferably 80 to 180 ° C, particularly preferably 100 to 150 ° C. The intermediate drying may preferably be followed by a heat treatment, optionally in the presence of steam. The temperature and duration of the heat treatment can vary over a wide range.

Die Temperatur bei der Hitzebehandlung beträgt in Gegenwart von Wasserdampf bevorzugt 100 bis 130 °C, besonders bevorzugt 102 bis 120 °C. Wird die Behandlung ohne Wasserdampf durchgeführt, beträgt die Behandlungstemperatur bevorzugt 150 bis 240 °C, besonders bevorzugt 175 bis 210 °C.The temperature in the heat treatment in the presence of water vapor is preferably 100 to 130 ° C, particularly preferably 102 to 120 ° C. If the treatment is carried out without steam, the treatment temperature is preferably 150 to 240 ° C, particularly preferably 175 to 210 ° C.

Die Dauer der Hitzebehandlung beträgt bevorzugt 15 Sekunden bis 60 Minuten, besonders bevorzugt 2 bis 45 Minuten und ganz besonders bevorzugt 5 bis 30 Minuten.The duration of the heat treatment is preferably 15 seconds to 60 minutes, more preferably 2 to 45 minutes, and most preferably 5 to 30 minutes.

Vorzugsweise werden die Farbstoffentwicklerkomponente, Echtfärbebasen und Echtfärbesalze jeweils in Form einer wäßrigen Lösung eingesetzt. Die nachfolgende Kupplung dieser Komponenten zu einem Azofarbstoff auf dem Vliesstoff erfolgt ebenfalls bevorzugt in wäßriger Lösung.Preferably, the dye developer component, Echtfärbebasen and Echtfärbesalze are each used in the form of an aqueous solution. The subsequent coupling of these components to an azo dye on the nonwoven fabric is also preferably carried out in aqueous solution.

Hierzu kann es erforderlich sein, die eingesetzten Komponenten zunächst nach üblichen, dem Fachmann bekannten Verfahren in Lösung zu bringen, wie z.B. für entsprechende Farbstoffentwicklerkomponenten in "Rath-Lehrbuch der Textilchemie, Springer Verlag Berlin, Heidelberg, New York, 3. Auflage 1972, Seite 549 beschrieben.For this purpose, it may be necessary to bring the components used first by customary methods known to those skilled in the art, for example for corresponding dye developer components in "Rath textbook of textile chemistry, Springer Verlag Berlin, Heidelberg, New York, 3rd edition 1972, page 549 described.

Die Behandlung des Vliesstoffes mit wenigstens einem Echtfärbesalz oder wenigstens einer Echtfärbebase und die Kupplung der Farbstoffentwicklerkomponente mit dem Echtfärbesalz oder der Echtfärbebase, nach deren Diazotierung, auf dem Vliesstoff kann ebenfalls bevorzugt nach dem Ausziehverfahren oder dem Klotzverfahren, gegebenenfalls mit Zwischentrocknung und gegebenenfalls nachfolgender Hitzebehandlung, ggf. in Gegenwart von Wasserdampf, durchgeführt werden, wobei jeweils sowohl die Behandlungsdauer als auch die Behandlungstemperatur in Abhängigkeit von dem jeweiligen Verfahren variieren können.The treatment of the nonwoven fabric with at least one Echtfärbesalz or at least one Echtfärbebase and the coupling of the dye developer component with the Echtfärbesalz or Echtfärbebase, after the diazotization, on the nonwoven fabric may also preferably by the exhaust or the padding process, optionally with intermediate drying and optionally subsequent heat treatment, if necessary in the presence of water vapor, wherein both the treatment time and the treatment temperature may vary depending on the particular method.

Im Ausziehverfahren beträgt die Temperatur bevorzugt -10 bis 130 °C, besonders bevorzugt 0 bis 60 °C und ganz besonders bevorzugt 5 bis 30 °C. Die Behandlungsdauer im Ausziehverfahren beträgt bevorzugt 5 bis 120 Minuten, besonders bevorzugt 10 bis 60 Minuten und ganz besonders bevorzugt 15 bis 45 Minuten.In the exhaust process, the temperature is preferably -10 to 130 ° C, more preferably 0 to 60 ° C and most preferably 5 to 30 ° C. The treatment time in the exhaustion process is preferably 5 to 120 minutes, more preferably 10 to 60 minutes and most preferably 15 to 45 minutes.

Im Klotzverfahren beträgt die Temperatur bevorzugt -10 bis 60 °C, besonders bevorzugt 0 bis 30 °C Die Behandlungsdauer im Klotzverfahren ist üblicherweise sehr kurz und beträgt vorzugsweise nicht mehr als 10 Sekunden.In the padding process, the temperature is preferably -10 to 60 ° C, particularly preferably 0 to 30 ° C. The treatment time in the padding process is usually very short and is preferably not more than 10 seconds.

Sofern anschließend eine Zwischentrocknung und/oder eine Hitzebehandlung, gegebenenfalls in Anwesenheit von Wasserdampf erfolgt, können diese jeweils unter den vorstehend angegebenen Bedingungen durchgeführt werden.If then an intermediate drying and / or a heat treatment, optionally in the presence of water vapor, these can each be carried out under the conditions given above.

Sofern der Vliesstoff mit einem oder mehreren der vorstehend genannten Entwicklungsfarbstoffe bedruckt wird, kann dies nach üblichen, dem Fachmann bekannten Druckverfahren erfolgen.If the nonwoven fabric is printed with one or more of the abovementioned development dyes, this can be done by customary printing processes known to the person skilled in the art.

Vorzugsweise wird hierzu zunächst die Farbstoffentwicklerkomponente nach einem der vorstehend genannten Färbeverfahren auf den Vliesstoff aufgebracht oder mit Hilfe eines üblichen, dem Fachmann bekannten Verfahren aufgedruckt.For this purpose, the dye developer component is preferably first applied to the nonwoven fabric by one of the above-mentioned dyeing methods or printed by means of a customary process known to the person skilled in the art.

Anschließend wird dann die jeweilige Echtfärbebase oder das Echtfärbesalz, gegebenenfalls unter Einsatz einer Schablone zur Erzeugung eines Musters auf den Vliesstoff aufgedruckt.Subsequently, the respective Echtfärbebase or Echtfärbesalz, optionally using a template to produce a pattern on the nonwoven fabric is printed.

Vorzugsweise erfolgt das Bedrucken des Vliesstoffes gemäß einem Direktdruckverfahren, vorzugsweise gemäß einem Filmdruckverfahren, besonders bevorzugt gemäß dem Rotationsfilm- oder Flachfilmdruckverfahren, oder gemäß dem Ink-Jet-Verfahren.Preferably, the printing of the nonwoven fabric according to a direct printing method, preferably according to a film printing method, more preferably according to the rotary film or flat film printing method, or according to the ink-jet method.

An das Bedrucken des Vliesstoffes kann sich bevorzugt eine Zwischentrocknung und gegebenenfalls eine nachfolgende Hitzebehandlung, gegebenenfalls in Gegenwart von Wasserdampf, anschließen, die jeweils bevorzugt unter den vorstehend angegebenen Bedingungen durchgeführt werden können.The printing of the nonwoven fabric may preferably be followed by intermediate drying and, if appropriate, subsequent heat treatment, if appropriate in the presence of steam, which in each case may preferably be carried out under the conditions indicated above.

Falls das Bedrucken des beschriebenen Vliesstoffes unter Verwendung von Druckpasten erfolgt, können diese nach üblichen, dem Fachmann bekannten Methoden hergestellt werden und neben der jeweiligen Farbstoffentwicklerkomponente bzw. der Echtfärbebase oder des Echtfärbesalzes auch weitere übliche Hilfsmittel enthalten, die bevorzugt ausgewählt werden können aus der Gruppe bestehend aus Verdickungsmitteln, Vernetzern, Weichmachern, Entschäumern, Netzmitteln und Feuchtigkeitsvermittlern. Ferner ist es auch möglich, aus der Echtfärbebase das entsprechende Diazoniumsalz in der Druckpaste durch Diazotierung zu erzeugen.If the printing of the described nonwoven fabric using printing pastes, they can be prepared by conventional methods known in the art and in addition to the respective dye developer component or Echtfärbebase or Echtfärbesalzes also contain other conventional auxiliaries, which can be preferably selected from the group from thickeners, crosslinkers, plasticizers, defoamers, wetting agents and moisture promoters. Furthermore, it is also possible from the Echtfärbebase to generate the corresponding diazonium salt in the printing paste by diazotization.

Vorzugsweise enthalten die Druckpasten neben der jeweiligen Farbstoffentwicklerkomponente bzw. der Echtfärbebase oder des Echtfärbesalzes als weiteren Bestandteil nur ein oder mehrere Verdickungsmittel, die bevorzugt ausgewählt werden können aus der Gruppe der natürlichen oder synthetischen Verdickungsmittel. Natürliche Verdickungsmittel können bevorzugt ausgewählt werden aus der Gruppe umfassend gegebenenfalls partiell abgebaute Stärke, Pflanzengummen, Johannisbrotkernmehl, veretherte Polysaccharide und Alginate. Synthetische Verdickungsmittel können vorzugsweise ausgewählt werden aus der Gruppe von wasserlöslichen carboxygruppenhaltigen Polymerisaten, die bevorzugt aus (Meth)acrylsäure und/oder Maleinsäurenahydrid bestehen können.Preferably, the printing pastes contain, in addition to the respective dye developer component or the Echtfärbebase or Echtfärbesalzes as another ingredient only one or more thickening agents, which can be preferably selected from the group of natural or synthetic thickeners. Natural thickeners may preferably be selected from the group comprising optionally partially degraded starch, vegetable gums, locust bean gum, etherified polysaccharides and alginates. Synthetic thickeners may preferably be selected from the group of water-soluble carboxyl group-containing polymers, which may preferably consist of (meth) acrylic acid and / or maleic acid hydride.

Des weiteren ist es auch möglich, einer der Druckpasten ein Reservierungsmittel zuzusetzen, das die Kupplung zwischen der Farbstoffentwicklerkomponente und der Echtfärbebase oder dem Echtfärbesalz verhindert, so daß auf dem zu bedruckenden Vliesstoff ein Muster entsteht.Furthermore, it is also possible to add a reservation agent to one of the printing pastes, which prevents the coupling between the dye developer component and the Echtfärbebase or the Echtfärbesalz, so that a pattern is formed on the nonwoven to be printed.

Gegebenenfalls kann sich der Kupplung der Komponenten zum Azofarbstoff eine Nachbehandlung des Vliesstoffes durch Erhitzen oder Behandlung mit Wasserdampf, auch bei erhöhter Temperatur anschließen. Die Behandlung mit Wasserdampf - das Nachdämpfen - erfolgt bevorzugt bei einer Temperatur von 100 bis 130 °C, vorzugsweise bei 102 bis 120 °C, das Erhitzen (Nachfixieren) bei einer Temperatur von 150 bis 240 °C, vorzugsweise bei 175 bis 210 °C. Die Dauer der Behandlung kann jeweils bevorzugt 10 Sekunden bis 30 Minuten, besonders bevorzugt 30 Sekunden bis 15 Minuten, ganz besonders bevorzugt 2 Minuten bis 10 Minuten betragen.Optionally, the coupling of the components to the azo dye can be followed by aftertreatment of the nonwoven fabric by heating or treatment with water vapor, even at elevated temperature. The treatment with steam - the post-fuming - is preferably carried out at a temperature of 100 to 130 ° C, preferably at 102 to 120 ° C, the heating (post-fixing) at a temperature of 150 to 240 ° C, preferably at 175 to 210 ° C. , The duration of the treatment may in each case preferably be 10 seconds to 30 minutes, particularly preferably 30 seconds to 15 minutes, very particularly preferably 2 minutes to 10 minutes.

Dem Färben und/oder Bedrucken des Vliesstoffes kann sich eine Reinigung des Vliesstoffes, vorzugsweise durch Spülen mit Wasser oder einer wäßrigen Lösung enthaltend Natriumhydrosulfit und Natriumhydroxid, auch bei erhöhter Temperatur, und/oder gegebenenfalls ein Seifen des Vliesstoffes anschließen, wobei die Bedingungen selbstverständlich so zu wählen sind, daß der aufgebrachte Azofarbstoff nicht wieder vollständig zerstört wird.The dyeing and / or printing of the nonwoven fabric may be followed by a cleaning of the nonwoven fabric, preferably by rinsing with water or an aqueous solution containing sodium hydrosulfite and sodium hydroxide, even at elevated temperature, and / or optionally soaps the nonwoven fabric, the conditions of course so too choose that the applied azo dye is not completely destroyed again.

Zur Erhöhung der Farbtiefe kann nach dem Färben und/oder Bedrucken im Zuge der Ausrüstung eine Behandlung des gefärbten und/oder bedruckten Vliesstoffes mit einem farbvertiefenden Hilfsmittel erfolgen. Als farbvertiefende Mittel kommen dabei sämtliche Chemikalien in Frage, die den Brechungswinkel des Lichtes auf der Oberfläche des Vliesstoffes, z.B. durch Bildung eines Films, so verändern, daß der Berechungsindex zwischen der Luft und dem Vliesstoff einen Wert größer 1 aufweist. Geeignete Chemikalien sind beispielsweise Polyacrylate, Polyurethane und Polysiloxane, die beispielsweise unter der Bezeichnung Badena® Eco 282, Finistrol® KSE-D, Baypret® USV und Arristan® 64 am Markt käuflich erhältlich sind. Sofern der gebildete Film aus Chemikalien besteht, welche die Farbstoffe auch gegen äußere Einflüsse schützen, wie z.B. Badena® Eco 282, so kann gleichzeitig auch eine Verbesserung der Farbechtheit erzielt werden.To increase the color depth, a treatment of the dyed and / or printed nonwoven fabric with a color-intensifying aid can be carried out after dyeing and / or printing in the course of the finishing. As color-intensifying agents, all chemicals are considered which can measure the refraction angle of the light on the surface of the nonwoven fabric, e.g. by forming a film, so that the calculation index between the air and the nonwoven fabric has a value greater than 1. Suitable chemicals are, for example, polyacrylates, polyurethanes and polysiloxanes which are commercially available, for example, under the name Badena® Eco 282, Finistrol® KSE-D, Baypret® USV and Arristan® 64. If the film formed consists of chemicals which protect the dyes also against external influences, such. Badena® Eco 282, at the same time an improvement in color fastness can be achieved.

Das farbvertiefende Hilfsmittel kann nach üblichen, dem Fachmann bekannten Methoden aufgebracht werden. Vorzugsweise kann das farbvertiefende Hilfsmittel mit Hilfe des Klotzverfahrens bei einem pH-Wert von 2 bis 12, vorzugsweise von 3 bis 9, besonders bevorzugt von 4 bis 8 auf das textile Material aufgebracht und bei Temperaturen von 40 bis 180 °C, vorzugsweise 100 bis 160 °C während einer Dauer von 1 Sekunde bis 120 Minuten, bevorzugt von 5 Sekunden bis 45 Minuten, besonders bevorzugt von 30 Sekunden bis 2 Minuten fixiert werden. Die jeweils geeingete Menge des farbvertiefenden Mittels kann variieren und kann vom Fachmann durch einfach Vorversuche ermittelt werden. Für Badena® Eco 282 beträgt die geeignete Menge vorzugsweise 10 bis 100 g/l Flotte, besonders bevorzugt 20 bis 50 g/l Flotte.The color-intensifying aid can be applied by customary methods known to the person skilled in the art. The color-intensifying aid may preferably be applied to the textile material at a pH of from 2 to 12, preferably from 3 to 9, particularly preferably from 4 to 8, using the padding process and at temperatures of from 40 to 180 ° C., preferably from 100 to 160 ° C for a period of 1 second to 120 minutes, preferably from 5 seconds to 45 minutes, more preferably from 30 Seconds can be fixed up to 2 minutes. The particular amount of color-enhancing agent that is suitable can vary and can be determined by the person skilled in the art by simple preliminary tests. For Badena® Eco 282, the suitable amount is preferably 10 to 100 g / l of liquor, more preferably 20 to 50 g / l of liquor.

Der erfindungsgemäß bedruckte und/oder gefärbte Vliesstoff aus ungesplitteten und/oder zumindest teilweise gesplitteten Mikrofasern und/oder Mikrofilamenten aus synthetischen Polymeren enthaltend wenigstens eine Polyesterkomponente und wenigstens eine Polyamidkomponente und gegebenenfalls wenigstens eine Polyurethankomponente zeichnet sich durch gute bis sehr gute Farbechtheiten, auch nach Hitzebehandlung, insbesondere durch gute bis sehr gute Wasch-, Schweiß-, Wasser- und Lichtechtheiten sowie durch gute Reibechtheiten aus.The printed and / or dyed nonwoven fabric according to the invention made of unsplit and / or at least partially split microfibers and / or microfilaments of synthetic polymers comprising at least one polyester component and at least one polyamide component and optionally at least one polyurethane component is characterized by good to very good color fastness, even after heat treatment, in particular by good to very good washing, welding, water and light fastness and good rubbing fastness.

Der nach dem erfindungsgemäßen Verfahren gefärbte und/oder bedruckte Vliesstoff eignet sich daher insbesondere zur Herstellung von Bekleidung, Heimtextilien, Futterstoffen, vorzugsweise für Gepäckstücke, sowie zur Herstellung von Textilprodukten im Bereich der Medizin und/oder Hygiene.The nonwoven fabric dyed and / or printed by the method according to the invention is therefore particularly suitable for the production of clothing, home textiles, linings, preferably for luggage, as well as for the production of textile products in the field of medicine and / or hygiene.

Ein weiterer Gegenstand der vorliegenden Erfindung ist daher die Verwendung wenigstens eines erfindungsgemäß gefärbten und/oder bedruckten Vliesstoffes zur Herstellung von Bekleidung, als Heimtextilien, als Futterstoffe, vorzugsweise Futterstoffe für Gepäckstücke, wie z.B. Koffer oder Taschen, sowie als textiles Material im Bereich der Medizin und/oder Hygiene.Another object of the present invention is therefore the use of at least one dyed and / or printed nonwoven fabric according to the invention for the production of clothing, as home textiles, as lining materials, preferably linings for luggage, such as e.g. Suitcases or bags, as well as textile material in the field of medicine and / or hygiene.

Durch das gleichzeitige Färben der verschiedenen Kunststoffkomponenten des zur Farbgebung eingesetzten Vliesstoffes mit nur einer Farbstoffklasse können gegenüber den aus dem Stand der Technik bekannten Verfahren u.a.Due to the simultaneous dyeing of the various plastic components of the nonwoven fabric used for coloring with only one dye class can be compared to the known from the prior art method, inter alia

Reinigungsschritte eingespart werden, was einerseits die Menge der produzierten Abwässer verringert und andererseits ein schnelleres und somit auch kostengünstigeres Färben und/oder Bedrucken der beschriebenen Vliesstoffe ermöglicht.Cleaning steps are saved, which on the one hand reduces the amount of wastewater produced and on the other hand allows faster and thus more cost-effective dyeing and / or printing of the nonwoven fabrics described.

Die Lichtechtheit des erfindungsgemäß gefärbten und/oder bedruckten textilen synthetischen Materials wurde gemäß EN ISO 105 B02, die Waschechtheit bei 40 °C, auch nach Hitzebehandlung, nach EN ISO 105 C06 A2S, die Beständigkeit gegenüber Wasser nach EN ISO 104 E01, die Beständigkeit gegenüber Schweiß nach EN ISO 104 E04 und die Beständigkeit gegenüber mechanischem Reiben gemäß EN ISO 105 X12 bestimmt.The lightfastness of the dyed and / or printed synthetic textile material according to the invention was, according to EN ISO 105 B02, the wash fastness at 40 ° C, even after heat treatment, according to EN ISO 105 C06 A2S, the resistance to water according to EN ISO 104 E01, the resistance to Welding according to EN ISO 104 E04 and resistance to mechanical rubbing in accordance with EN ISO 105 X12.

Im folgenden wird die Erfindung anhand von Beispielen erläutert. Diese Erläuterungen sind lediglich beispielhaft und schränken den allgemeinen Erfindungsgedanken nicht ein.In the following the invention will be explained by way of examples. These explanations are merely exemplary and do not limit the general inventive concept.

Beispiel 1:Example 1:

Ein Spinnvliesstoff mit einem Flächengewicht von 100 g/m2 bestehend aus zum Teil gesplitteten Mikrofasern aus 70 Gew.-% Polyethylenterephthalat und 30 Gew.-% Polyamid 66 mit einem Titer von ca. 0,15 dtex wurde im Ausziehverfahren mit einer wäßrigen Hydroxynaphthoesäure-Derivat-Zubereitung, die C.I. Azoic Coupling Component 5 enthielt, (Handelsname: Naphtol AS-G, DyStar) grundiert und anschließend mit einer Echtfärbesalz-Zubereitung, die C.I. Azoic Diazo Component 33 (Salt) (Handelsname: Echtrotsalz FRN, DyStar) enthielt, gekuppelt.A spunbonded nonwoven having a weight per unit area of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of nylon 66 having a titre of about 0.15 dtex was extracted by means of an aqueous hydroxynaphthoic acid Primer formulation containing CI Azoic Coupling Component 5 (trade name: Naphtol AS-G, DyStar) and then blended with a true color salt preparation containing CI Azoic Diazo Component 33 (Salt) (trade name: fast-release salt FRN, DyStar), coupled.

Das Naphtol wurde hierzu zunächst mittels Kaltlöseverfahren gelöst, wobei 1,4 g des Naphtols mit 10 ml einer 10 Gew.-%-igen Rizinusöl-Lösung und 5 ml einer 10 Gew.-%-igen Natriumhydroxid-Lösung angeteigt und mit 20 ml 60 °C warmem Wasser, das 0,0175 g eines Komplexbildners auf Basis von Trinatriumnitrilotriacetat enthielt, übergossen wurden.The naphthol was first dissolved by means of cold dissolving method, with 1.4 g of naphthol with 10 ml of a 10 wt .-% - castor oil solution and 5 ml of a 10 wt .-% - sodium hydroxide solution pasted in with 20 ml of 60 ° C warm water containing 0.0175 g of a complexing agent based on trisodium nitrilotriacetate, were poured over.

Anschließend wurde mit 135 ml Wasser mit einer Temperatur von 20 °C, welches 0,0825 g eines Komplexbildners auf Basis von Trinatriumnitrilotriacetat und 30 ml einer 10 Gew.-%-igen Natriumchlorid-Lösung enthielt aufgefüllt und 5 min bei 40 °C gerührt.It was then filled with 135 ml of water at a temperature of 20 ° C, which contained 0.0825 g of a complexing agent based on trisodium nitrilotriacetate and 30 ml of a 10 wt .-% - sodium chloride solution and stirred at 40 ° C for 5 min.

Mit der so erhaltenen Lösung wurden anschließend 10 g des Spinnvliesstoffes bei einem Flottenverhältnis von 1:20 grundiert. Dazu wurde die Lösung zusammen mit dem Vliesstoff in einen Färbebecher gegeben und mit 1,5 °C/min auf 130°C aufgeheizt. Nach einer Verweilzeit von 30 min bei 130°C wurde mit 1,5 °C/min auf 80°C abgekühlt und 10 min bei einem Flottenverhältnis von 1:10 mit 199,8 ml 40 °C warmem Wasser, das 0,2 ml einer 32 Gew.-%-igen Natriumhydroxidlösung, 10 g Natriumchlorid und 0,1 g eines Komplexbildners auf Basis von Trinatriumnitrilotriacetat enthielt, gespült.10 g of the spun-bonded nonwoven fabric were then primed with the solution thus obtained at a liquor ratio of 1:20. For this purpose, the solution was placed together with the nonwoven fabric in a dyeing cup and heated to 130 ° C at 1.5 ° C / min. After a residence time of 30 min at 130 ° C was cooled at 1.5 ° C / min to 80 ° C and 10 min at a liquor ratio of 1:10 with 199.8 ml of 40 ° C warm water containing 0.2 ml a 32 wt .-% sodium hydroxide solution, 10 g of sodium chloride and 0.1 g of a complexing agent based on trisodium nitrilotriacetat, rinsed.

Die Entwicklung mit der Echtfärbesalz-Zubereitung wurde ebenfalls im Ausziehverfahren bei einem Flottenverhältnis von 1:10 sofort nach der Grundierung durchgeführt. Dazu wurden 0,9144 g des Echtrotsalzes mit 94 ml 10 °C warmen Wasser, das 6 ml einer 0,15 Gew.-%-igen Lösung eines Dispergiermittels auf Basis eines oxethylierten höheren Alkohols und 1 g Natriumacetat enthielt, gelöst. Der naptholgrundierte Vliesstoff wurde in einem Färbeapparat mit dieser Lösung bei 20 °C für 30 min behandelt und anschließend 15 min bei 70°C mit einer Lösung, die 1 g/l Natriumcarbonat und 0,5 g/l eines Dispergiermittels auf Basis eines oxethylierten höheren Alkohols enthielt, geseift.The development with the true color salt preparation was also carried out in the exhaust process at a liquor ratio of 1:10 immediately after the primer. To this was dissolved 0.9144 g of the fast-drying salt with 94 ml of warm water at 10 ° C., which contained 6 ml of a 0.15% by weight solution of a dispersant based on an ethoxylated higher alcohol and 1 g of sodium acetate. The napthol-primed nonwoven fabric was treated in a dyeing machine with this solution at 20 ° C for 30 min and then for 15 min at 70 ° C with a solution containing 1 g / l of sodium carbonate and 0.5 g / l of a dispersant based on an ethoxylated higher alcohol, soaped.

Die entsprechende Lichtechtheit des gefärbten Vliesstoffs sowie die Waschechtheit bei 40 °C, die Beständigkeit gegenüber Wasser, die Beständigkeit gegenüber Schweiß und die Beständigkeit gegenüber mechanischem Reiben sind in der Tabelle 1 angegeben.The corresponding light fastness of the dyed nonwoven fabric and the wash fastness at 40 ° C, the resistance to water, the resistance to perspiration and the resistance to mechanical rubbing are given in Table 1.

Beispiel 2:Example 2:

Ein Spinnvliesstoff mit einem Flächengewicht von 100 g/m2 bestehend aus zum Teil gesplitteten Mikrofasern aus 70 Gew.-% Polyethylenterephthalat und 30 Gew.-% Polyamid 66 mit einem Titer von ca. 0,15 dtex wurde analog zu Bespiel 1 grundiert und gespült.A spunbonded nonwoven having a basis weight of 100 g / m 2 consisting of partially split microfibers of 70 wt .-% polyethylene terephthalate and 30 wt .-% polyamide 66 with a titer of about 0.15 dtex was primed and rinsed analogously to Example 1 ,

Die Entwicklung mit der Echtfärbesalz-Zubereitung gemäß Beispiel 1 wurde unmittelbar nach dem Grundieren im Klotzverfahren durchgeführt. Dazu wurden 6,92 g der Echtfärbesalz-Zubereitung mit 99 ml 15 °C warmen Wassers, das 1 ml einer 7 Gew.-%-igen Lösung eines Dispergiermittels auf Basis eines oxethylierten höheren Alkohols und 1 g Natriumacetat enthielt, gelöst. Der pH-Wert wurde mit 60 Gew.-%-iger Essigsäure auf 5 eingestellt. Diese Lösung wurde bei 20 °C auf den grundierten, feuchten Vliesstoff aufgeklotzt. Die Flottenaufnahme betrug 100 Gew.-%, bezogen auf das Gewicht des eingesetzten Vliesstoffes. Anschließend wurde der Vliesstoff bei 20 °C für 60 Sekunden mit Umluft behandelt und wie in Beispiel 1 angegeben geseift.Development with the true color salt preparation according to Example 1 was carried out immediately after priming in the padding process. To this was dissolved 6.92 g of the true color salt preparation with 99 ml of 15 ° C. warm water containing 1 ml of a 7% strength by weight solution of a dispersant based on an ethoxylated higher alcohol and 1 g of sodium acetate. The pH was adjusted to 5 with 60% strength by weight acetic acid. This solution was padded at 20 ° C on the primed, wet nonwoven fabric. The liquor pickup was 100 wt .-%, based on the weight of the nonwoven fabric used. Subsequently, the nonwoven fabric was treated at 20 ° C for 60 seconds with circulating air and soaped as indicated in Example 1.

Die entsprechende Lichtechtheit des gefärbten Vliesstoffs sowie die Waschechtheit bei 40 °C, die Beständigkeit gegenüber Wasser, die Beständigkeit gegenüber Schweiß und die Beständigkeit gegenüber mechanischem Reiben sind in der Tabelle 1 angegeben.The corresponding light fastness of the dyed nonwoven fabric and the wash fastness at 40 ° C, the resistance to water, the Resistance to perspiration and resistance to mechanical rubbing are given in Table 1.

Beispiel 3:Example 3:

Ein Spinnvliesstoff mit einem Flächengewicht von 100 g/m2 bestehend aus zum Teil gesplitteten Mikrofasern aus 70 Gew.-% Polyethylenterephthalat und 30 Gew.-% Polyamid 66 mit einem Titer von ca. 0,15 dtex wurde im Ausziehverfahren mit einer flüssigen Hydroxybenzocarbazolcarbonsäure-Zubereitung, die C.I. Azoic Coupling Component 13 enthielt, (Handelsname: Naphtol AS-SG fl., DyStar) grundiert und anschließend mit einer Echtfärbesalz-Zubereitung, die C.I. Azoic Diazo Component 33 (Salt) (Handelsname: Echtrotsalz FRN, DyStar) enthielt, gekuppelt. Die Grundierung wurde im Ausziehverfahren bei einem Flottenverhältnis von 1:20 durchgeführt. 3,5 g des Naphtols wurden mit 196,5 ml 40 °C warmem Wasser, das 2 g Natriumchlorid und 0,1 g eines Komplexbildners auf Basis von Trinatriumnitrilotriacetat enthielt übergossen und 5 min bei 40 °C gerührt. Mit der so hergestellten Lösung wurden 10 g des Vliesstoffes bei einem Flottenverhältnis von 1:20 grundiert. Dazu wurde die Lösung zusammen mit dem Vliesstoff in einen Färbebecher gegeben und mit 1,5 °C/min auf 130 °C aufgeheizt. Nach einer Verweilzeit von 30 min bei 130 °C wurde mit 1,5 °C/min auf 80 °C abgekühlt und 10 min bei einem Flottenverhältnis von 1:20 mit 199,8 ml 40 °C warmem Wasser, das 0,2 ml einer 32 Gew.-%-igen Natriumhydroxidlösung, 4 g Natriumchlorid und 0,1 g eines Komplexbildners auf Basis von Trinatriumnitrilotriacetat enthielt, gespült.A spunbonded nonwoven fabric having a weight per unit area of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 having a titer of about 0.15 dtex was prepared by exhaustion with a liquid hydroxybenzocarbazolecarboxylic acid. Primer, and then treated with a true color salt preparation containing CI Azoic Diazo Component 33 (Salt) (trade name: fast-release salt FRN, DyStar), containing CI Azoic Coupling Component 13 (trade name: Naphtol AS-SG fl., DyStar); coupled. The primer was carried out by exhaustion at a liquor ratio of 1:20. 3.5 g of the naphthol were poured over with 196.5 ml of 40 ° C warm water containing 2 g of sodium chloride and 0.1 g of a complexing agent based on trisodium nitrilotriacetate and stirred at 40 ° C for 5 min. With the solution thus prepared 10 g of the nonwoven fabric were primed at a liquor ratio of 1:20. For this purpose, the solution was placed together with the nonwoven fabric in a dyeing cup and heated to 130 ° C at 1.5 ° C / min. After a residence time of 30 min at 130 ° C was cooled at 1.5 ° C / min to 80 ° C and 10 min at a liquor ratio of 1:20 with 199.8 ml of 40 ° C warm water containing 0.2 ml a 32 wt .-% sodium hydroxide solution, 4 g of sodium chloride and 0.1 g of a complexing agent based on trisodium nitrilotriacetate, rinsed.

Die Entwicklung mit der Echtfärbesalz-Zubereitung wurde ebenfalls im Ausziehverfahren bei einem Flottenverhältnis von 1:10 sofort nach der Grundierung durchgeführt. Dazu wurden 1,01 g des Echtrotsalzes mit 99,95 ml 15 °C warmen Wasser, das 0,05 g eines Dispergiermittels auf Basis eines oxethylierten höheren Alkohols und 1 g Natriumacetat enthielt, übergossen. Der pH-Wert wurde mit 60 Gew.-%-iger Essigsäure auf 4,5 eingestellt. Der naphtolgrundierte Vliesstoff wurde in einem Färbeapparat mit dieser Lösung bei 20 °C 30 min behandelt und anschließend 15 min bei 70°C mit einer Lösung, die 1 g/l Natriumcarbonat und 0,5 g/l eines Dispergiermittels auf Basis eines oxethylierten höheren Alkohols enthielt, geseift.The development with the true color salt preparation was also carried out in the exhaust process at a liquor ratio of 1:10 immediately after the primer. To this was added 1.01 g of the fast-drying salt with 99.95 ml of 15 ° C warm water containing 0.05 g of a dispersant based on a ethoxylated higher alcohol and 1 g of sodium acetate, poured over. The pH was adjusted to 4.5 with 60% by weight acetic acid. The naphtol-primed nonwoven fabric was treated in a dyeing machine with this solution at 20 ° C for 30 minutes and then for 15 minutes at 70 ° C with a solution containing 1 g / l of sodium carbonate and 0.5 g / l of a dispersant based on an ethoxylated higher alcohol contained, soaped.

Die entsprechende Lichtechtheit des gefärbten Vliesstoffs sowie die Waschechtheit bei 40 °C, die Beständigkeit gegenüber Wasser, die Beständigkeit gegenüber Schweiß und die Beständigkeit gegenüber mechanischem Reiben sind in der Tabelle 1 angegeben.The corresponding light fastness of the dyed nonwoven fabric and the wash fastness at 40 ° C, the resistance to water, the resistance to perspiration and the resistance to mechanical rubbing are given in Table 1.

Beispiel 4:Example 4:

Ein Spinnvliesstoff mit einem Flächengewicht von 100 g/m2 bestehend aus zum Teil gesplitteten Mikrofasern aus 70 Gew.-% Polyethylenterephthalat und 30 Gew.-% Polyamid 66 mit einem Titer von ca. 0,15 dtex wurde im Klotzverfahren mit einer flüssigen Hydroxybenzocarbazolcarbonsäure-Zubereitung, die C.I. Azoic Coupling Component 13 enthielt, (Handelsname: Naphtol AS-SG fl., DyStar) grundiert und anschließend mit einer Echtfärbesalz-Zubereitung, die C.I. Azoic Diazo Component 33 (Salt) (Handelsname: Echtrotsalz FRN, DyStar) enthielt, gekuppelt.A spunbonded nonwoven fabric having a weight per unit area of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 having a titer of about 0.15 dtex was treated in the padding process with a liquid hydroxybenzocarbazolecarboxylic acid. Primer, and then treated with a true color salt preparation containing CI Azoic Diazo Component 33 (Salt) (trade name: fast-release salt FRN, DyStar), containing CI Azoic Coupling Component 13 (trade name: Naphtol AS-SG fl., DyStar); coupled.

Dazu wurden 3 g des Naphtols in eine 90 °C heiße Lösung, die neben 65 ml Wasser 0,05 g eines Komplexbildners auf Basis von Trinatriumnitrilotriacetat und 0,5 ml eines Dispergiermittels auf Basis eines Naphtalinsulfonsäure-Formaldehyd-Kondensats enthielt eingerührt, anschließend wurde mit kochendem Wasser auf 100 ml aufgefüllt. Diese Lösung wurde bei 90-95 °C auf 10 g des Vliesstoffs aufgeklotzt- die Flottenaufnahme betrug ca. 100 Gew.-%, bezogen auf das Gewicht des eingesetzten Vliesstoffes, dann wurde 90 Sekunden bei 140 °C zwischengetrocknet.To 3 g of Naphtols in a 90 ° C hot solution containing in addition to 65 ml of water, 0.05 g of a complexing agent based on trisodium nitrilotriacetate and 0.5 ml of a dispersant based on a Naphtalinsulfonsäure-formaldehyde condensate stirred then with made up to 100 ml with boiling water. This solution was padded at 90-95 ° C to 10 g of the nonwoven fabric - the liquor pickup was about 100 wt .-%, based on the weight of the nonwoven fabric used, then 90 seconds at 140 ° C was inter-dried.

Zur Herstellung der Entwicklungsflotte, die mittels Klotzverfahren auf den grundierten Vliesstoff aufgebracht wurde, wurden zunächst 3,9 g des Echtfärbesalzes mit 58,5 ml 15 °C warmem Wasser und 1 ml einer 3 Gew.-%-igen Lösung eines Dispergiermittels auf Basis eines oxethylierten höheren Alkohols enthielt, gelöst und mit 40,5 ml 15 °C warmem Wasser, das 0,1 ml eines Dispergiermittels auf Basis eines oxethylierten höheren Alkohols und 1 g Natriumacetat enthielt, übergossen. Der pH-Wert wurde mit 60 Gew.-%-iger Essigsäure auf 5,5 eingestellt.To prepare the developing liquor, which was applied by padding method to the primed nonwoven fabric, first 3.9 g of Echtfärbesalzes with 58.5 ml of 15 ° C warm water and 1 ml of a 3 wt .-% - solution of a dispersant based on a dissolved with 40.5 ml of 15 ° C warm water containing 0.1 ml of a dispersant based on an ethoxylated higher alcohol and 1 g of sodium acetate, poured over. The pH was adjusted to 5.5 with 60% by weight acetic acid.

Die grundierte Ware wurde mit dieser Lösung bei 20°C geklotzt - Die Flottenaufnahme lag bei 100 Gew.-%, bezogen auf den eingsetzten Vliesstoff, dann wurde bei 20 °C 60 Sekunden mit Umluft behandelt, bei 200°C 180 Sekunden nachfixiert und wie in Beispiel 1 angegeben geseift.The primed goods were padded with this solution at 20 ° C - The liquor pickup was 100 wt .-%, based on the einsetzten nonwoven fabric, then 60 seconds was treated with circulating air at 20 ° C, post-fixed at 200 ° C for 180 seconds and as soaped in Example 1.

Die entsprechende Lichtechtheit des gefärbten Vliesstoffs sowie die Waschechtheit bei 40 °C, die Beständigkeit gegenüber Wasser, die Beständigkeit gegenüber Schweiß und die Beständigkeit gegenüber mechanischem Reiben sind in der Tabelle 1 angegeben.The corresponding light fastness of the dyed nonwoven fabric and the wash fastness at 40 ° C, the resistance to water, the resistance to perspiration and the resistance to mechanical rubbing are given in Table 1.

Beispiel 5:Example 5:

Ein Spinnvliesstoff mit einem Flächengewicht von 100 g/m2 bestehend aus zum Teil gesplitteten Mikrofasern aus 70 Gew.-% Polyethylenterephthalat und 30 Gew.-% Polyamid 66 mit einem Titer von ca. 0,15 dtex wurde zunächst mit Naphtol AS (Dystar), einer wäßrigen Hydroxynaphthoesäurezubereitung, die C.I. Azoid Coupling Component 2 enthielt, als Farbstoffentwicklerkomponente geklotzt. Anschließend wurde der Vliesstoff bei 140 °C für 90 Sekunden getrocknet.A spunbonded nonwoven having a basis weight of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 having a titer of about 0.15 dtex was first treated with Naphtol AS (Dystar). , an aqueous hydroxynaphthoic acid preparation containing CI Azoid Coupling Component 2, as a dye developer component padded. Subsequently, the nonwoven fabric was dried at 140 ° C for 90 seconds.

Dann wurde eine Stammpaste A aus 500 g Diagum A8 (BF Goodrich, Diamalt, Barcelona, Spanien), ein Verdickungsmittel auf Basis von Johannisbrotmehl, 491 g Wasser und 9 g Natriumnitrit und eine Stammpaste B aus 500 g Diagum A8, 440 g Wasser und 60 g Phosphorsäure hergestellt. Anschließend wurde zur Herstellung einer Druckpaste 30 g der Echtbase Echtrot B (Dystar), C.I. Azoic Diazo Component 5, verdünnt mit 70 g Wasser, in 600 g der Stammpaste A eingerührt und mit 300 g der Stammpaste B versetzt. Die so erhaltene Paste wurde anschließend für 5 Minuten nachgerührt, so daß eine Diazotierung der Echtbase erfolgte. Die so erhaltene Paste wurde dann unter Verwendung einer Schablone nach dem Siebdruckverfahren auf den zuvor mit der Farbstoffentwicklerkomponente geklotzten Vliesstoff aufgebracht. Zur Entfernung der nichtgekuppelten Echtbase wurde der Vliesstoff dann für 30 Minuten bei einer Temperatur von 90 °C mit Natriumdithionit in wäßriger Natronlauge behandelt und anschließend mit Calgon T und Soda geseift.Then, a stock paste A was prepared from 500 g of Diagum A8 (BF Goodrich, Diamalt, Barcelona, Spain), a locust bean thickener, 491 g of water and 9 g of sodium nitrite, and a stock paste B of 500 g of Diagum A8, 440 g of water and 60 g g phosphoric acid produced. Subsequently, to produce a printing paste, 30 g of Echtbase Echtrot B (Dystar), C.I. Azoic Diazo Component 5, diluted with 70 g of water, stirred into 600 g of stock paste A and admixed with 300 g of stock paste B. The paste thus obtained was then stirred for 5 minutes, so that a diazotization of the true base was carried out. The thus-obtained paste was then screen-printed on the nonwoven fabric previously padded with the dye developer component using a stencil. To remove the uncoupled Echtbase the nonwoven fabric was then treated for 30 minutes at a temperature of 90 ° C with sodium dithionite in aqueous sodium hydroxide solution and then soaped with Calgon T and soda.

Beispiel 6:Example 6:

Ein Spinnvliesstoff mit einem Flächengewicht von 100 g/m2 bestehend aus zum Teil gesplitteten Mikrofasern aus 70 Gew.-% Polyethylenterephthalat und 30 Gew.-% Polyamid 66 mit einem Titer von ca. 0,15 dtex wurde zunächst mit einer wäßrigen Lösung von Naphtol AS (Dystar), einer Hydroxynaphthoesäurezubereitung, die C.I. Azoic Coupling Component 2 enthielt, als Farbstoffentwicklerkomponente geklotzt. Anschließend wurde der Vliesstoff bei 140 °C für 90 Sekunden getrocknet. Dann wurde der so vorbehandelte Vliesstoff unter Verwendung einer Schablone mit einer Paste aus 200 g Aluminiumsulfat-Monohydrat, 200 g Wasser und 600 g Celluloseether bedruckt und dann für 3 Minuten bei einer Temperatur von 120 °C getrocknet.A spunbonded nonwoven having a weight per unit area of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 having a titer of about 0.15 dtex was initially treated with an aqueous solution of naphthol AS (Dystar), a hydroxynaphthoic acid preparation containing CI Azoic Coupling Component 2, padded as a dye developer component. Subsequently, the nonwoven fabric was dried at 140 ° C for 90 seconds. Then, the thus pretreated nonwoven fabric was prepared by using a stencil with a paste of 200 g of aluminum sulfate monohydrate, 200 g of water and 600 g Printed cellulose ether and then dried for 3 minutes at a temperature of 120 ° C.

Anschließend wurde eine Lösung enthaltend 24 g/l Variaminsalz Blau BN (Dystar, C.I. Azoic Diazo Component 35), gelöst mit 1 g/l eines Dispergiermittels Dispersogen ASN auf Basis eines ethoxylierten höheren Alkohols (Clariant) aufgeklotzt. An den Stellen des Vliesstoffes, wo das Aluminiumsulfat zuvor aufgebracht worden war, erfolgt keine Kuppplung, so daß der resultierende Vliesstoff ein weißes Muster aufwies. Der Luftgang betrug 60 Sekunden.Subsequently, a solution containing 24 g / l of Variam salt Blue BN (Dystar, C.I. Azoic Diazo Component 35) dissolved with 1 g / l of a dispersant Dispersogen ASN based on an ethoxylated higher alcohol (Clariant) was padded. At the locations of the nonwoven fabric where the aluminum sulfate had previously been applied, no coupling occurs, so that the resulting nonwoven fabric had a white pattern. The aisle was 60 seconds.

Anschließend wurde der Vliesstoff mittels Natriumhydrosulfit und Natronlauge reduktiv gereinigt, mit heißem fließenden Wasser gespült und dann kochend mit einer Lösung enthaltend jeweils 1 g/l Naphtopon E (Bayer AG, Deutschland), Calgon T (Benkieser) und Soda geseift.The nonwoven fabric was then reductively cleaned by means of sodium hydrosulfite and sodium hydroxide solution, rinsed with hot running water and then boiled with a solution containing 1 g / l Naphtopon E (Bayer AG, Germany), Calgon T (Benkieser) and soda.

Beispiel 7:Example 7:

Ein Spinnvliesstoff mit einem Flächengewicht von 100 g/m2 bestehend aus zum Teil gesplitteten Mikrofasern aus 70 Gew.-% Polyethylenterephthalat und 30 Gew.-% Polyamid 66 mit einem Titer von ca. 0,15 dtex wurde zunächst mit einer wäßrigen Lösung von Naphtol AS (Dystar), einer Hydroxynaphthoesäurezubereitung, die C.I. Azoic Coupling Component 2 enthielt, als Farbstoffentwicklerkomponente geklotzt. Anschließend wurde der Vliesstoff bei 140 °C für 90 Sekunden getrocknet. Dann wurde der so vorbehandelte mit einer Paste aus 60 g Echtorgangesalz GGD, 3 g des Dispergiermittels Dispersogen ASN, 317 g Wasser, 70 g Aluminiumsulfat-Monohydrat, 550 g Tylose H 300 bedruckt und dann für 3 Minuten bei einer Temperatur von 120 °C getrocknet.A spunbonded nonwoven having a weight per unit area of 100 g / m 2 consisting of partially split microfibers of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 having a titer of about 0.15 dtex was initially treated with an aqueous solution of naphthol AS (Dystar), a hydroxynaphthoic acid preparation containing CI Azoic Coupling Component 2, padded as a dye developer component. Subsequently, the nonwoven fabric was dried at 140 ° C for 90 seconds. Then, the thus pretreated was printed with a paste of 60 g Echtorgangesalz GGD, 3 g of the dispersant Dispersogen ASN, 317 g of water, 70 g of aluminum sulfate monohydrate, 550 g Tylose H 300 and then dried for 3 minutes at a temperature of 120 ° C. ,

Anschließend wurde eine Lösung enthaltend 24 g/l Variaminsalz Blau BN, gelöst mit 1 g/l eines Dispergiermittels Dispersogen ASN aufgeklotzt. An den Stellen des Vliesstoffes, wo das Aluminiumsulfat zuvor aufgebracht worden war, erfolgt keine Kuppplung mit dem Variaminblausalz, jedoch mit dem Echtorangesalz GGD, so daß der resultierende Vliesstoff ein Muster aufweist. Der Luftgang betrug 60 Sekunden.Subsequently, a solution containing 24 g / l of variant salt blue BN dissolved with 1 g / l of a dispersant Dispersogen ASN was padded. At the locations of the nonwoven fabric where the aluminum sulfate had previously been applied, coupling with the variham blue salt but with the true orange salt GGD is not effected so that the resulting nonwoven fabric has a pattern. The aisle was 60 seconds.

Anschließend wurde der Vliesstoff mit Hilfe von Natriumhydrosulfit und Natronlauge reduktiv gereinigt, mit heißem fließenden Wasser gespült und dann kochend mit einer Lösung enthaltend jeweils 1 g/l Naphtopon E (Bayer AG), Calgon T (Benkieser) und Soda geseift. Tabelle 1: Beispiel 1: Farbe: Gelb Beispiel 2: Farbe: Gelb Beispiel 3: Farbe: Graubraun Beispiel 4. Farbe: Graubraun Wäsche 40°C EN ISO 105 C06 A2S 4S / 4C 4S / 4C 4S / 4C 4S / 4C Wäsche 40°C EN ISO 105 C06 A2S nach Hitzebehandlung 1 min 150°C 4S / 4C 4S / 4C 4S / 4C 4S / 4C Wäsche 40°C EN ISO 105 C06 A2S nach Hitzebehandlung 1 min 180°C 4S / 4C 4S / 4C 4S / 4C 4S / 4C Wasser EN ISO 104 E01 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C Schweiß sauer EN ISO 104 E04 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C Schweiß alkalisch EN ISO 104 E04 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C Reibechtheit EN ISO 105 X12 4 trocken / 3-4 naß 4 trocken / 3-4 naß 4 trocken / 3 naß 3-4 trocken / 3 naß Lichtechtheit EN ISO 105 802 - - 5 5 The nonwoven fabric was then reductively cleaned with the aid of sodium hydrosulfite and sodium hydroxide solution, rinsed with hot flowing water and then boiled with a solution containing 1 g / l Naphtopon E (Bayer AG), Calgon T (Benkieser) and soda. <b> Table 1: </ b> Example 1: Color: yellow Example 2: Color: yellow Example 3: Color: greyish brown Example 4. Color: greyish brown Wash 40 ° C EN ISO 105 C06 A2S 4S / 4C 4S / 4C 4S / 4C 4S / 4C Wash 40 ° C EN ISO 105 C06 A2S after heat treatment 1 min 150 ° C 4S / 4C 4S / 4C 4S / 4C 4S / 4C Wash 40 ° C EN ISO 105 C06 A2S after heat treatment 1 min 180 ° C 4S / 4C 4S / 4C 4S / 4C 4S / 4C Water EN ISO 104 E01 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C Sweat sour EN ISO 104 E04 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C Sweat alkaline EN ISO 104 E04 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C 4-5S / 4-5C Rubbing fastness EN ISO 105 X12 4 dry / 3-4 wet 4 dry / 3-4 wet 4 dry / 3 wet 3-4 dry / 3 wet Lightfastness EN ISO 105 802 - - 5 5

S = Anbluten von Begleitgewebe / C = Farbänderung der Probe
1 Sehr schlecht
5 Sehr gutS = bleeding of accompanying tissue / C = color change of the sample
1 Very bad
5 very good

Claims (39)

  1. Dyed and/or printed nonwoven composed of unsplit and/or at least partly split microfibres and/or microfilaments composed of synthetic polymers comprising at least one polyester component and at least one polyamide component and, if desired, at least one polyurethane component, characterized in that the dyed and/or printed nonwoven is dyed and/or printed with at least one azo dye generated on the nonwoven.
  2. Nonwoven according to Claim 1, characterized in that it consists of at least one polyester component and at least one polyamide component.
  3. Nonwoven according to Claim 2, characterized in that it consists of 5% to 95% by weight of at least one polyester component and 95 to 5% by weight of at least one polyamide component, preferably of 15% to 85% by weight of at least one polyester component and 85% to 15% by weight of at least one polyamide component, more preferably of 70% to 30% by weight of at least one polyester component and 30% to 70% by weight of at least one polyamide component.
  4. Nonwoven according to any one of Claims 1 to 3, characterized in that the polyamide component is selected from the group consisting of nylon 6, nylon 66 and nylon 11.
  5. Nonwoven according to any one of Claims 1 to 4, characterized in that the polyester component is selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polylactic acid, their mixtures and copolyesters.
  6. Nonwoven according to any one of Claims 1 to 5, characterized in that the linear density of the microfibres and/or microfilaments is ≤ 1 dtex, preferably 0.02 to 0.95 dtex, more preferably 0.05 to 0.85 and most preferably 0.1 to 0.5 dtex.
  7. Nonwoven according to any one of Claims 1 to 6, characterized in that it is a staple fibre nonwoven.
  8. Nonwoven according to any one of Claims 1 to 6, characterized in that it is a spunbonded nonwoven.
  9. Nonwoven according to any one of Claims 1 to 8, characterized in that it has a basis weight in the range from 15 to 400 g/m2, preferably in the range from 50 to 350 g/m2 and more preferably in the range from 80 to 200 g/m2.
  10. Process for dyeing and/or printing a nonwoven according to one or more of Claims 1 to 9, wherein this nonwoven is treated with at least one dye developer component at a temperature of ≥ 90°C and at least one fast colour salt or at least one fast colour base and the dye developer component is coupled with the fast colour salt or the fast colour base, after diazotization thereof, on the nonwoven.
  11. Process according to Claim 10, characterized in that the dye developer component is selected from the group consisting of arylamides of aromatic hydroxy carboxylic acids, arylamides of keto acids and hydroxynaphthyl ketones.
  12. Process according to Claim 11, characterized in that an arylamide of an aromatic hydroxy carboxylic acid is used and it is an amide of 2-hydroxy-3-naphthoic acid, preferably 2-hydroxy-3-naphthanilide, 2-hydroxy-3-naphthoic acid o-toluidide, 2-hydroxy-3-naphthoic acid 4,6-dimethoxy-3-chloroanilide, 2-hydroxy-3-naphthoic acid α-naphthylamide or [bis-2-hydroxy-3-naphthoic acid]dianiside, an amide of anthracene, preferably 2-hydroxy-3-anthracene carboxylic acid o-toluidide, an amide of carbazole, preferably 2-hydroxycarbazole-3-carboxylic acid 4'-chloroanilide or an amide of diphenylene oxide, preferably 3-hydroxydibenzofuran-2-carboxylic acid 2',5'-dimethoxyanilide.
  13. Process according to Claim 11, characterized in that an arylamide of a keto acid is used and it is diacetoacetic acid o-toluidide or terephthaloylbisacetic acid bis[2-methoxy-4-chloro-5-methylanilide].
  14. Process according to any one of Claims 10 to 13, characterized in that o-chloroaniline, o-nitroaniline, m-nitro-p-toluidine, 4-diethylsulphamido-1-amino-1-methoxybenzene, 4-chloro-2-aminodiphenyl ether, α-aminoanthraquinone, 4-amino-3-methoxyazabenzene, 4-amino-1-benzoylamino-3-methoxy-6-methylbenzene, o-dianisidine, 4-amino-4'-methoxydiphenylamine, 3,5-bistrifluoromethylaniline or 3-fluorosulphonylaniline is used as fast colour bases.
  15. Process according to any one of Claims 10 to 14, characterized in that the nonwoven is treated with the dye developer component by the exhaust process in the presence or absence of carriers.
  16. Process according to Claim 15, characterized in that the treatment temperature is in the range from 90 to 150°C and preferably in the range from 100 to 130°C.
  17. Process according to Claim 15 or 16, characterized in that the treatment time is in the range from 10 to 180 minutes, preferably in the range from 20 to 120 minutes and more preferably in the range from 25 to 60 minutes.
  18. Process according to any one of Claims 10 to 14, characterized in that the nonwoven is treated with the dye developer component by the pad process, if desired with subsequent interdrying and if desired subsequent heat treatment, if desired in the presence of water vapour.
  19. Process according to Claim 18, characterized in that the interdrying temperature is in the range from 80 to 180°C and preferably in the range from 100 to 150°C.
  20. Process according to Claim 18 or 19, characterized in that the interdrying time is in the range from 30 seconds to 10 minutes and preferably in the range from 2 minutes to 5 minutes.
  21. Process according to any one of Claims 18 to 20, characterized in that the heat treatment temperature is in the range from 100 to 130°C and preferably in the range from 102 to 120°C in the presence of water vapour and in the range from 150 to 240°C and preferably in the range from 175 to 210°C in the absence of water vapour.
  22. Process according to any one of Claims 18 to 21, characterized in that the treatment time is in the range from 15 seconds to 60 minutes, preferably in the range from 2 to 45 minutes and most preferably in the range from 5 to 30 minutes.
  23. Process according to any one of Claims 10 to 22, characterized in that the treatment with at least one fast colour salt or at least one fast colour base and/or the coupling of the fast colour salt or fast colour base, after diazotization thereof, on the nonwoven are effected by the exhaust process.
  24. Process according to Claim 23, characterized in that the treatment temperature is in the range from -10 to 130°C, preferably in the range from 0 to 60°C and more preferably in the range from 5 to 30°C.
  25. Process according to Claim 23 or 24, characterized in that the treatment time is in the range from 5 to 120 minutes, preferably in the range from 10 to 60 minutes and more preferably in the range from 15 to 45 minutes.
  26. Process according to any one of Claims 10 to 22, characterized in that the treatment with at least one fast colour salt or at least one fast colour base and/or the coupling of the fast colour salt or of the fast colour base, after diazotization thereof, on the nonwoven are effected by the pad process, if desired with subsequent drying and if desired followed by a heat treatment.
  27. Process according to Claim 26, characterized in that the treatment time during the pad process is in the range from -10 to 60°C and preferably in the range from 0 to 30°C.
  28. Process according to Claim 26 or 27, characterized in that the treatment does not take more than 10 seconds.
  29. Process according to any one of Claims 26 to 28, characterized in that the subsequent drying is effected at 80 to 180°C and more preferably at 100 to 150°C.
  30. Process according to any one of Claims 26 to 29, characterized in that the drying time is in the range from 30 seconds to 10 minutes and preferably in the range from 2 to 5 minutes.
  31. Process according to any one of Claims 26 to 30, characterized in that the heat treatment is effected at 100 to 130°C and preferably at 102 to 120°C in the presence of water vapour and at 150 to 240°C and preferably at 175 to 210°C without water vapour.
  32. Process according to any one of Claims 10 to 31, characterized in that the dye developer component and/or the fast colour base or the fast colour salt is printed onto the nonwoven.
  33. Process according to Claim 32, characterized in that printing is effected by a direct printing process, preferably by a screen printing process and more preferably by a rotary screen or flat screen printing process, or by the ink jet process.
  34. Process according to any one of Claims 10 to 33, characterized in that the dye developer component and/or the fast colour base or the fast colour salt are present in aqueous solution.
  35. Process according to any one of Claims 10 to 34, characterized in that the coupling of the dye developer component with the fast colour base or the fast colour salt is effected in aqueous solution.
  36. Use of at least one dyed and/or printed nonwoven according to any one of Claims 1 to 9 for producing clothing.
  37. Use of at least one dyed and/or printed nonwoven according to any one of Claims 1 to 9 as home textiles.
  38. Use of at least one dyed and/or printed nonwoven according to any one of Claims 1 to 9 as liners, preferably as liner in luggage items.
  39. Use of at least one dyed and/or printed nonwoven according to any one of Claims 1 to 9 as a textile material in the sector of medicine and/or hygiene.
EP02747447A 2001-07-24 2002-06-28 Dyed and/or printed non-woven fabric Expired - Lifetime EP1412578B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10135940 2001-07-24
DE10135940A DE10135940B4 (en) 2001-07-24 2001-07-24 Process for the production of dyed and / or printed nonwovens and their use
PCT/EP2002/007150 WO2003014464A1 (en) 2001-07-24 2002-06-28 Dyed and/or printed non-woven fabric

Publications (2)

Publication Number Publication Date
EP1412578A1 EP1412578A1 (en) 2004-04-28
EP1412578B1 true EP1412578B1 (en) 2006-01-04

Family

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Application Number Title Priority Date Filing Date
EP02747447A Expired - Lifetime EP1412578B1 (en) 2001-07-24 2002-06-28 Dyed and/or printed non-woven fabric

Country Status (5)

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US (1) US20040194234A1 (en)
EP (1) EP1412578B1 (en)
CN (1) CN1245552C (en)
DE (2) DE10135940B4 (en)
WO (1) WO2003014464A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8236385B2 (en) 2005-04-29 2012-08-07 Kimberly Clark Corporation Treatment of substrates for improving ink adhesion to the substrates
IT1404168B1 (en) * 2011-02-10 2013-11-15 Alcantara Spa PROCESS FOR DYEING IN CAPTURE OF A MANUFACTURING THAT INCLUDES A NON-WOVEN MICROFIBRATION FABRIC
US20140212618A1 (en) * 2013-01-30 2014-07-31 Milliken & Company Printed Textile Substrate and Process for Making
CN104674568B (en) * 2015-01-23 2017-01-25 郎溪飞马工业织品有限公司 Dyeing method of safety braid
US9840807B2 (en) 2015-03-10 2017-12-12 Charles Francis Luzon Process for dyeing textiles, dyeing and fortifying rubber, and coloring and revitalizing plastics
WO2020162347A1 (en) 2019-02-04 2020-08-13 イーグル工業株式会社 Sliding component and method for manufacturing sliding component
KR102634941B1 (en) 2019-02-04 2024-02-08 이구루코교 가부시기가이샤 sliding parts

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1154069B (en) * 1958-12-27 1963-09-12 Bayer Ag Process for the production of water-insoluble azo dyes on structures made of aromatic polyesters, in particular polyethylene terephthalates, synthetic polyamides and polyurethanes
US3081141A (en) * 1961-02-28 1963-03-12 Du Pont Ingrain dyeing with nitroso/amine condensates
NL294654A (en) * 1962-06-28
CH382338A (en) * 1963-02-22 1964-06-15 Rohner Ag Process for the production of water-insoluble azo dyes on textile structures made of linear aromatic polyesters, primarily polyethylene terephthalates
US3928314A (en) * 1969-11-27 1975-12-23 Ciba Geigy Ag One step process of preparing azo dyes by simultaneous diazotization and coupling at low pH
DE2231245C3 (en) * 1972-06-26 1980-11-13 Ciba-Geigy Ag, Basel (Schweiz) Process for dyeing and printing cellulose, linen, wool, silk, polyamides or leather with development mono- or disazo dyes
CH575505B5 (en) * 1974-03-28 1976-05-14 Ciba Geigy Ag
US4202815A (en) * 1977-03-21 1980-05-13 Rohner Ag Pratteln Concentrated powder or granular formulations dispersable in aqueous media
JPH07252427A (en) * 1994-03-14 1995-10-03 Mitsubishi Kasei Hoechst Kk Disazo dye
JPH09310287A (en) * 1996-05-23 1997-12-02 Toyobo Co Ltd Dyed structure made of polyester/polyamide conjugate-type ultrafine fiber and its production
FR2749860B1 (en) * 1996-06-17 1998-08-28 Freudenberg Spunweb Sa NON WOVEN TABLECLOTH FORMED OF VERY THIN CONTINUOUS FILAMENTS
DE10125843A1 (en) * 2000-11-27 2002-07-04 Freudenberg Carl Dyed and / or printed nonwoven

Also Published As

Publication number Publication date
DE10135940A1 (en) 2003-02-13
CN1245552C (en) 2006-03-15
EP1412578A1 (en) 2004-04-28
DE50205529D1 (en) 2006-03-30
US20040194234A1 (en) 2004-10-07
CN1535342A (en) 2004-10-06
WO2003014464A1 (en) 2003-02-20
DE10135940B4 (en) 2008-10-23

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